CN1281660C

CN1281660C - Hydrophilic Polymer containing silane couple end base and lithographic printing plate bottom material

Info

Publication number: CN1281660C
Application number: CNB02106881XA
Authority: CN
Inventors: 山崎纯明; 川村浩一
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2001-01-24
Filing date: 2002-01-24
Publication date: 2006-10-25
Anticipated expiration: 2022-01-24
Also published as: DE60215710T2; US20060073414A1; ATE344148T1; DE60215710D1; CN1367193A; US20020134266A1; US7001673B2; EP1226976A1; EP1226976B1

Abstract

A polymer compound includes i) a polymerization unit represented by - (CHR<3>-CR<4)<-L<1>-Y<1>))x- (CHR<5>-CR<6> (-L<2>-Y<2>))y-; and ii) a silane coupling group represented by -S- (CH2)n-Si- (R<1>)m(OR<2>)3-m, as a terminal of the polymer, wherein R<1>, R<2>, R<3>, R<4>, R<5>, R<6>, n, x, y, L<1>, L<2>, Y<1> and Y<2> are defined in the specification. A lithographic printing plate base includes: a support; and a hydrophilic layer containing solid particles to a surface of which a hydrophilic polymer is chemically bonded.

Description

The hydrophilic polymer and the lithographic plate ground that contain silane coupling end group

Background of invention

1, invention field

The present invention relates to a kind of new hydrophilic polymer with end group silane coupling group, this hydrophilic polymer can be used for as anti-fog coating, in the application of coating of anti-external contamination and so on, and can be used in the hydrophilic layer of lithographic plate ground.

The invention still further relates to a kind of lithographic plate ground, this ground contains a kind of new hydrophilic layer.More specifically, the present invention relates to a kind of lithographic plate ground, when it was used as Lighographic printing plate precursor, it can have high wetting ability, and can not damage the intensity of film.

2, description of the invention

Although known various hydrophilic polymers up to now, do not know any hydrophilic polymer with silane coupling end group.Because this hydrophilic polymer can be widely used in the application that comprises anti-fog coating and anti-external contamination coating and so on, therefore this polymkeric substance of great use.

The hydrophilic ground or the hydrophilic layer that use in lithographic plate up to now comprise anodized aluminum substrates, with be further to strengthen wetting ability, with as silicate, poly-(vinyl phosphonate) (referring to the open No.1853/1995 of Japanese Patent) or gather the resulting ground of the anodized aluminum substrates of prime treatment or the hydrophilic layer of (vinyl benzoic acid) and so on.People have carried out earnest research to the aluminum substrates and the hydrophilic layer of such hydrophilization.And, in the open No.101651/1984 of Japanese Patent, described in the undercoat that is generating photoactive layer, use the technology of the polymkeric substance that contains methylthio group.

On the other hand, people know about hydrophilic layer and are not used in metallic carrier as alumina supporter and so on, and are used for the technology as the resilient support of PET (polyethylene terephthalate) or rhodia carrier and so on.The example of hydrophilic layer comprises like this: disclosed hydrophilic layer in the open No.292558/1996 of Japanese Patent, and this hydrophilic layer comprises hydrophilic polymer and hydrophobic polymer, and can expand; Disclosed pet vector in EP 0709228, this carrier have the hydrophilic crosslinked silicate surfaces of micropore; With disclosed hydrophilic layer in open No.272087/1996 of Japanese Patent and No.507727/1996, these hydrophilic layers comprise hydrophilic polymer, and solidify with positive silicic acid tetraalkyl ester hydrolysate.

The generation of these hydrophilic layers provides lithographic plate, and they can obtain satisfactory printed matter, and is difficult for causing track down and recover stolen goods (making dirty) in the starting stage of printing.But, from the higher suitability angle of practical application, need a kind of Lighographic printing plate precursor, the hydrophilic layer of this precursor has higher wetting ability, even under stricter printing condition, can not peel off down, and the printed matter that obtains is not tracked down and recover stolen goods from carrier yet.Although people have known the water retention capacity by the increase hydrophilic layer, but make hydrophilic layer have higher wetting ability, but this technology causes following problem.Make the hydrophilic layer modification of correlation technique, when improving its water retention capacity, the swelling capacity of the hydrophilic layer that obtains like this strengthens, therefore, the membrane structure reduction, intensity reduces, and perhaps gives carrier sticking power.

Description of the invention

First purpose of the present invention provides a kind of new hydrophilic polymer, and this polymkeric substance has silane coupling end group, is used for the application as anti-fog coating and anti-external contamination coating and so on, is used for the hydrophilic layer of lithographic plate ground.

Second purpose of the present invention is to eliminate the problem of the existence in the relevant technologies.Promptly, second purpose provides a kind of plus or minus type lithographic plate ground, it has high wetting ability, and can not damage the film strength of hydrophilic layer, the performance of this lithographic plate ground is improved especially, can not cause the printing of tracking down and recover stolen goods, even the printed matter of under the printing condition of strictness, also can not tracked down and recover stolen goods (not making dirty).

According to first characteristics of the present invention, the invention provides hydrophilic polymer, it contains: i) usefulness-(CHR ³-CR ⁴(-L-Y))-expression polymerized unit; Ii) use-S-(CH ₂) _n-Si-(R ¹) _m(OR ²) _3-mThe silane coupling group of expression, as polymer terminal group, R wherein ¹, R ², R ³And R ⁴Represent hydrogen atom separately or have the alkyl of 1-8 carbon atom; M represents 0,1 or 2; N represents the integer among the 1-8; Y representative-N (R ⁷) (R ⁸) ,-OH ,-NHCOR ⁷,-COR ⁷,-CO ₂M or-SO ₃M, wherein R ⁷And R ⁸Represent hydrogen atom separately or have the alkyl of 1-8 carbon atom; M represent hydrogen atom, basic metal, alkaline-earth metal or; The weight-average molecular weight of this polymer compound is 1000-100000; L represents singly-bound or following linking group:

-CH ₂- -O-

-S-

-NH-

Hydrophilic polymer by chemical formula (1) expression comprises any one hydrogen atom, usefulness-S-(CH ₂) _n-Si-(R ¹) _m(OR ²) _3-mThe silane coupling group of expression, and polymerization starter are as the right side end group.

Weight-average molecular weight by the hydrophilic polymer of chemical formula (1) expression is 1 000-100 000, more preferably is 1 000-50 000, particularly preferably is 1 000-30 000.

When for example adding the present invention had the hydrophilic polymer of silane coupling end group on substrate surface, substrate surface was a highly-hydrophilic.For example, contain the wetting ability that the coating of polymkeric substance of the present invention can be given the substrate surface height toward ground coating.Even when water droplet attached to the coating ground on the time, water droplet is dispersed on the substrate surface equably.Therefore, this polymkeric substance can prevent effectively that glass, lens, mirror etc. from hazing, and the transparency of losing preventing through moisture guarantees that aspect the visibility meter in rainy weather also be useful.In addition, Urban dust, the products of combustion that in the gas of automobile and other dischargings, contains, as carbon black, and hydrophobic dirt material, fat and component as being discharged by sealing agent are difficult for being attached on the ground of coating.Even when such dirt is attached to the ground of coating, can be by rainwater or washing easily with its removal.

In order to realize second purpose of the present invention, the inventor has also carried out broad research.Therefore, they find, contain the hydrophilic layer that the solia particle of hydrophilic polymer modification has been used on its surface by generating on carrier, can obtain to have the lithographic plate ground of high-hydrophilic and don't loss film strength.Based on this discovery, finished the present invention.

Second characteristic the invention provides following material according to the present invention.

(1) contain the lithographic plate ground that carrier also forms hydrophilic layer thereon, hydrophilic layer contains solia particle, and hydrophilic polymer and microparticle surfaces chemical bonding.

(2) the lithographic plate ground described in above (1), it has a undercoat between carrier and hydrophilic layer.

Inventors adopt and give high hydrophilic technology and successfully solve these problems, and this technology is included in and forms hydrophilic layer, hydrophilic polymer and this solia particle surface chemistry bonding that contains solia particle on the carrier.In this press plate ground, solia particle is dense distribution on matrix, form surface irregularity, and microparticle surfaces is by the hydrophilic polymer modification.Because this structure, the water capacity easily is penetrated in the hydrophilic layer, and hydrophilic layer has the water retention capacity of very big improvement and outstanding wetting ability.And the hydrophilic polymer in the hydrophilic layer is also uncrosslinked.Therefore, hydrophilic layer is difficult for being expanded by water-soluble, film strength can not take place reduce, and also may have outstanding wetting ability.It is believed that, just can reach this effect of the present invention by reaching water retention capacity and sticking power, the two has alternative relation each other in relevant technologies.

Can form photosensitive or thermographic layer on this basis.This imaging layer comprises positive sensitization or negative photosensitive composition.

Lithographic plate ground of the present invention preferably has a undercoat between carrier and hydrophilic layer.This undercoat can improve the sticking power between carrier and the hydrophilic layer.

In lithographic plate ground of the present invention, preferably made carrier surface (solid surface) roughen.Make the coarse nonimaging district that can make of solid surface have the enhanced wetting ability, this causes hydrophobicity/wetting ability to have very big difference, and further improves and in press do not cause the performance of tracking down and recover stolen goods.

Detailed description of the present invention

Hydrophilic polymer of the present invention is explained as follows in detail.

In this hydrophilic polymer, R ¹, R ², R ³, R ⁴, R ⁵And R ⁶Represent hydrogen atom separately or have alkyl up to 8 carbon atoms.Having preferred embodiment up to 8 carbon atom alkyl comprises and contains straight chain, side chain or the cyclic alkyl of 8 carbon atoms at the most.Its specific examples comprises methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, sec.-propyl, isobutyl-, the second month in a season-butyl, tert-butyl, isopentyl, neo-pentyl, 1-methyl butyl, isohexyl, 2-ethylhexyl, 2-methyl hexyl and cyclopentyl.These alkyl can have one or more substituting groups.Preferably, R ¹, R ², R ³, R ⁴, R ⁵And R ⁶Each is hydrogen atom, methyl or ethyl naturally.

L ¹And L ²Represent singly-bound or organic linking group by oneself.Organic linking group is represented the multivalence linking group that is made of non-metallic atom.For example, it is by 1-60 carbon atom, a 0-10 nitrogen-atoms, a 0-50 Sauerstoffatom, a 1-100 hydrogen atom and 0-20 the linking group that sulphur atom constitutes.The specific examples of linking group comprises following structural unit and group, and each comprises two or more these unitary combinations.

-CH ₂- -O-

-S- -NH-

Y ¹And Y ²Representative-N (R by oneself ⁷) (R ⁸) ,-OH ,-NHCOR ⁷,-COR ⁷,-CO ₂M or-SO ₃M, wherein R ⁷And R ⁸Represent hydrogen atom by oneself or have the alkyl of 1-8 carbon atom, M represents hydrogen atom, basic metal, alkaline-earth metal or father-in-law.-N (R ⁷) (R ⁸) in, R ⁷And R ⁸Can interosculate forms ring, and this ring may be to contain one or more heteroatomic heterocycles that are selected from oxygen, sulphur, nitrogen and other atoms.

R ⁷And R ⁸Represent hydrogen atom by oneself or have the alkyl of 1-8 carbon atom.This alkyl preferably has straight chain, side chain or the cyclic alkyl of 1-8 carbon atom.The example comprises methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, sec.-propyl, isobutyl-, the second month in a season-butyl, tert-butyl, isopentyl, neo-pentyl, 1-methyl butyl, isohexyl, 2-ethylhexyl, 2-methyl hexyl and cyclopentyl.

R ⁷And R ⁸In these alkyl also can contain one or more substituting groups.Work as R ⁷And R ⁸When alkyl had substituting group, substituted alkyl was combined with alkylidene group by substituting group and constitutes, and the monovalent nonmetallic atomic group except hydrogen atom is as substituting group.The preferred embodiment of this monovalent atoms group comprises halogen atom (F; Br; Cl; I); hydroxyl; alkoxyl group; aryloxy; sulfydryl; alkylthio; arylthio; alkyl dithio base; aryl dithio base; amino; the N-alkylamino; N; the N-ammonia diaryl base; N-alkyl-N-arylamino; acyloxy; carbamoyloxy; N-alkyl carbamoyloxy base; N-arylamino methanoyl; N; N-dialkyl amido methanoyl; N; N-ammonia diaryl base methanoyl; N-alkyl-N-arylamino methanoyl; alkyl sulfide oxygen base; aryl sulphur oxygen base; the acyl group thio group; amido; the N-alkyl amido; N-propenyl amido; urea groups; N '-alkyl urea groups; N '; N '-dialkyl group urea groups; N '-aryl-ureido; N '; N '-diaryl urea groups; N '-alkyl-N '-aryl-ureido; N-alkyl urea groups; the N-aryl-ureido; N '-alkyl-N-alkyl urea groups; N '-alkyl-N-aryl-ureido; N '; N '-dialkyl group-N-alkyl urea groups; N '; N '-dialkyl group-N-aryl-ureido; N '-aryl-N-alkyl urea groups; N '-aryl-N-aryl-ureido; N '; N '-diaryl-N-alkyl urea groups; N '; N '-diaryl-N-aryl-ureido; N '-alkyl-N '-aryl-N-alkyl urea groups; N '-alkyl-N '-aryl-N-aryl-ureido; alkoxycarbonyl amino; aryloxycarbonyl amino; N-alkyl-N-alkoxycarbonyl amino; N-alkyl-N-aryloxycarbonyl amino; N-aryl-N-alkoxycarbonyl amino; N-aryl-N-aryloxycarbonyl amino; formyl radical; acyl group; carboxyl; alkoxy carbonyl; aryloxycarbonyl; formamyl; the N-alkyl-carbamoyl; N-dialkyl amido formyl radical; the N-aryl-amino-carbonyl; N, N-ammonia diaryl base formyl radical; N-alkyl-N-aryl-amino-carbonyl; alkyl sulphinyl; aryl sulfonyl kia; alkyl sulphonyl; aryl sulfonyl; sulfonic group (SO ₃H) and conjugate base (being called " sulfonation group " afterwards), alkoxyl group alkylsulfonyl, aryl sulfonyl, sulfonamido, N-amino-alkyl sulfinyl, N; N-dialkyl group sulfonamido, N-aromatic yl sodium sulfonamido, N; N-diaryl sulfonamido, N-alkyl-N-aromatic yl sodium sulfonamido, sulfamyl, N-alkylsulfamoyl group, N; N-dialkyl sulfamine, N-ammonia aryl sulfonyl, N, N-ammonia diaryl alkylsulfonyl, N-alkyl-N-ammonia aryl sulfonyl, phosphoryl (PO ₃H ₂) and the conjugate base group (be referred to as " (O afterwards ^-) ₂P (O)-) group "), dialkyl phosphine acyl group (PO ₃(alkyl) ₂), diaryl phosphono (PO ₃(alkyl) ₂), alkylaryl phosphono (PO ₃(alkyl) (aryl)), monoalkyl phosphono (PO ₃H (alkyl)) and conjugate base (be referred to as " alkyl-(O afterwards ^-) ₂P (O)-group "), single aryl phosphine acyl group (PO ₃H (aryl)) and the conjugate base group (be referred to as " aryl-(O afterwards ^-) ₂P (O)-group "), phosphonato (OPO ₃H ₂) and conjugate base group (being referred to as " phosphonatoxy group " afterwards), dialkyl phosphine acyloxy (OPO ₃(alkyl) ₂), diaryl phosphonato (OPO ₃(aryl) ₂), alkylaryl phosphonato (OPO ₃(alkyl) (aryl)), monoalkyl phosphonato (OPO ₃H (alkyl)) and grip base groups (being referred to as " alkyl phosphonatoxy group " afterwards), single aryl phosphine acyloxy (OPO altogether ₃H (aryl)) and grip base groups (being referred to as " aryl phosphonatoxy group " afterwards), cyano group, nitro, aryl, thiazolinyl and alkynyl altogether.

The example of moieties comprises the above alkyl of enumerating in these substituting groups; the example of the aryl moiety in those substituting groups comprises phenyl; xenyl; naphthyl; tolyl; xylyl; 2; 4,6 trimethylphenyls; cumenyl; chloro-phenyl-; bromophenyl; chloromethyl phenyl; hydroxyphenyl; p-methoxy-phenyl; ethoxyl phenenyl; Phenoxyphenyl; the acetoxyl group phenyl; the benzoyl phenyl; the methylthio group phenyl; the thiophenyl phenyl; the methylamino phenyl; dimethylaminophenyl; the acetylamino phenyl; carboxyl phenyl; the methoxycarbonyl phenyl; the ethoxyl phenenyl carbonyl; the phenyloxycarbonyl phenyl; N-phenyl amino formyl radical phenyl; phenyl; cyano-phenyl; sulfur phenenyl; the sulfonato phenyl; the phosphono phenyl and-(O ^-) ₂P (O)-phenyl.The example of thiazolinyl comprises vinyl, 1-propenyl, 1-butylene base, cinnamyl and 2-chloro-1-vinyl.The example of alkynyl comprises ethynyl, 1-proyl, ethyl acetylene base and trimethyl silyl ethynyl.In G1CO-, represent the G1 example of acyl group to constitute by hydrogen atom and abovementioned alkyl and aryl.In those substituted radicals; halogen atom (F; Br; Cl; I); alkoxyl group; aryloxy; alkylthio; arylthio; the N-alkylamino; N; the N-dialkyl amido; acyloxy; N-alkyl carbamoyloxy base; N-arylamino methanoyl; amido; formyloxy; acyl group; carboxyl; alkoxy carbonyl; aryloxycarbonyl; formamyl; the N-alkyl-carbamoyl; N; N-dialkyl amido formyl radical; the N-aryl-amino-carbonyl; N-alkyl-N-aryl-amino-carbonyl; sulfo group; sulfonato; sulfamyl; the N-alkylsulfamoyl group; N, the N-dialkyl sulfamine; the N-ammonia aryl sulfonyl; N-alkyl-N-ammonia aryl sulfonyl; phosphono;-(O ^-) ₂P (O)-, dialkyl phosphine acyl group, diaryl phosphono, monoalkyl phosphono, alkyl-(O ^-) ₂P (O)-, single aryl phosphine acyl group, aryl-(O ^-) ₂P (O)-, phosphonato, phosphonatoxy base, aryl and thiazolinyl are preferred than other groups.

In addition, monoradical is as R ⁷And R ⁸Can be substituted alkyl separately.Comprise the organic residue of divalence at such alkylene moiety example that is substituted in the alkyl, they can by as more than remove a hydrogen atom in each C1-20 alkyl of enumerating, preferably, remove the organic residue of divalence that a hydrogen atom obtains in C3-12 branched alkylidene and the C5-10 ring alkylidene group from C1-12 straight chain alkylene.The suitable example that is combined the substituted alkyl that is generated by substituting group with alkylidene group comprises chloromethyl; brooethyl; the 2-chloroethyl; trifluoromethyl; methoxymethyl; methoxyethoxyethyl; the allyloxy methyl; phenoxymethyl; methylthiomethyl; the tolyl sulphomethyl; the ethylamino ethyl; the diethylamino propyl group; the morpholino propyl group; acetoxy-methyl; the benzoyl methyl; N-cyclohexyl carboxyamide oxygen base ethyl; N-phenyl amino methanoyl ethyl; the acetylamino ethyl; N-ethylamino benzonitrile acyl group aminopropyl; the 2-hydroxyethyl; the 2-hydroxypropyl; the carboxyl propyl group; the methoxycarbonyl ethyl; the allyloxy carbonyl butyl; chloro phenyloxycarbonyl methyl; the carbamyl ylmethyl; N-methylamino formyl radical ethyl; N; N-dipropyl-carbamyl ylmethyl; N-(p-methoxy-phenyl) formamyl ethyl; N-methyl-N-(thio-phenyl) carbamyl ylmethyl; the sulfo-butyl; the sulfonato butyl; the sulfamyl butyl; N-ethyl sulfamyl methyl; N, N-dipropyl sulfamyl propyl group; N-tolyl sulfamyl propyl group; N-methyl-N-(phosphono phenyl) sulfamyl octyl group; the phosphono butyl;-(O ^-) ₂P (O)-hexyl, diethyl phosphonyl butyl, xenyl phosphono-propyl group, methylphosphine acyl group butyl, methyl-(O ^-) ₂P (O)-butyl, three phosphono hexyls, tolyl-(O ^-) ₂P (O)-hexyl, phosphonato-propyl group ,-(O ^-) ₂P (O)-oxygen Ji Dingji, benzyl, phenelyl, α-Jia Jibianji, 1-methyl isophthalic acid-phenylethyl, right-methyl-benzyl, cinnamyl, allyl group, 1-propenyl methyl, crotyl, 2-methacrylic, 2-methyl-propenyl methyl, 2-propenyl, crotyl and 3-butenyl.

The specific examples of hydrophilic polymer of the present invention is as follows.But the present invention should not be subjected to the restriction of these embodiment.

When these embodiment clearly do not limit the right side end group of each polymkeric substance, an arbitrary hydrogen atom can be provided, identical silane coupling base is as left side end group and polymerization starter.Following polymkeric substance 1-17 has shown as polymer backbone (main polymer chain) and the compound that uses as right side silane coupling end group.Following polymkeric substance 18-23 has shown as copolymer skeleton (each index number of multipolymer is represented molar percent) and the compound that uses as right side silane coupling end group.

In order to carry out radical polymerization, can use any known method with synthetic hydrophilic polymer of the present invention.For example, can use Kobunshi No Gosei To Hanno 1 (association edits by polymer science, Kyoritsu Shuppan) at Shin Kobunshi Jikken-gaku 3; Shin Jikken Kagaku Koza 19, KobunshiKagaku (I) (is edited by Japanese Chemical Society, Maruzen); With Busshitus Kogaku Koza, the method for describing among the KobunshiGosei Kagaku (Tokyo Denki university press portion).

More specifically, hydrophilic polymer of the present invention can synthesize through radical polymerization with the unsaturated compound of following general formula (2) or (3) expression with the hydrosulphonyl silane compound that following general formula (4) is represented with one or more each and obtains.Because hydrosulphonyl silane compound (4) has chain transfer ability, so the radical polymerization effect can be created in the polymkeric substance that adds the silane coupling group in the polymer backbone.

(R ¹) _m(OR ²) _3-m-Si-(CH ₂) _n-S-H (4)

In chemical formula (2), (3) and (4), R ¹-R ⁶, L ¹, L ², Y ¹, Y ², n has and the identical implication of chemical formula (1) with m.These compounds can buy from the market, and can synthesize easily and obtain.

(reactive mode)

With in the hydrosulphonyl silane compound of general formula (4) expression and the reaction of one or more unsaturated compounds with general formula (2) or (3) expression, to reactive mode without any special restriction.For example, in the presence of radical initiator, or during with irradiation such as high voltage mercury lamp reactive system, preferably carry out bulk reaction, solution reaction, suspension reaction (supernatant liquid reaction) etc.Polymerization process also is not particularly limited, and suitably select suitable method according to purpose, for example batch processes (comprise portioning wherein or add the method for raw material in succession), semicontinuous or continuation method etc.Especially, wherein portioning adds each method (being commonly referred to " portioning loading process " later on) with one or more unsaturated compounds of general formula (2) or (3) expression, the method (being called " method of addition " later on) that wherein adds unsaturated compound in succession is preferred polymerization process, in these processes homopolymerization takes place because can suppress unsaturated compound effectively.For example, people know, when the hydrosulphonyl silane compound of for example using general formula (4) to represent carries out Raolical polymerizable (mol ratio 1: 1) with one or more unsaturated compounds of representing with general formula (2) or (3) in a step, although the homopolymer with the unsaturated compound of general formula (2) or (3) expression depends on the polymeric reaction condition that comprises temperature, this situation of about 10 weight % homopolymer growing amounts still exists.On the contrary, for example these starting compounds use the reinforced method of portioning (for example dividing for three steps fed in raw material) when carrying out Raolical polymerizable, the amount of the homopolymer of representing with general formula (2) or (3) under uniform temp and other polymerizing conditions that unsaturated compound generates can be reduced to below the 10 weight % at an easy rate so.

(reactant ratio)

Ratio with general formula (4) the hydrosulphonyl silane compound of representing and one or more unsaturated compound interreactions of representing with general formula (2) or (3) does not have particular restriction yet.But, preferably use unsaturated compound and the unsaturated compound of representing by general formula (3) by general formula (2) expression, its amount separately for example is that every mole of hydrosulphonyl silane compound with general formula (4) expression is the 0.5-50 mole.Its reason is when the ratio of reactant exceeds this scope, and side reaction takes place easily, and this may cause the productive rate of hydrolyzable silane compound to reduce.Therefore, use the amount separately of the question response unsaturated compound of general formula (2) and (3) expression to be respectively, every mole of hydrosulphonyl silane compound with general formula (4) expression is preferably the 1-45 mole, more preferably the 5-40 mole.

Unsaturated compound with general formula (2) expression does not have particular restriction with the ratio that the unsaturated compound of representing with general formula (3) reacts yet.But with the usage quantity of the unsaturated compound of general formula (2) expression preferably, per 100 moles of unsaturated compound total amounts of using general formula (2) and (3) to represent respectively are the 100-1 mole, more preferably are the 100-5 moles.

(radical initiator)

Radical initiator is azo radical initiator or organo-peroxide preferably, more preferably the azo radical initiator.Preferred azo radical initiator example comprises 2,2 '-azobis isobutyronitrile, 1,1 '-azo two (hexanaphthene-1-nitrile), 2, two (the 4-methoxyl groups-2 of 2 '-azo, the 4-methyl pentane nitrile), 2,2 '-azo two (2, the 4-methyl pentane nitrile), 2,2 '-azo two (2-methylbutyronitrile), 1-[(1-cyano group-1-methylethyl) azo] methane amide, 2-phenylazo-4-methoxyl group-2, the 4-methyl pentane nitrile, dimethyl 2,2 '-azo two (2 Methylpropionic acid ester), 2, two (2-methyl-the N-[1 of 2 '-azo, 1-two (hydroxymethyl)-2-hydroxyethyl] propionic acid amide), 2, two { 2-methyl-the N-[1 of 2 '-azo, 1-two (methylol) ethyl propionic acid amide] }, 2,2 '-azo two [2-methyl-N-(2-hydroxyethyl) propionic acid amide], 2, two [2-(5-methyl-2-tetrahydroglyoxaline-2-yl) propane] dihydrochlorides of 2 '-azo, 2, two [2-(2-tetrahydroglyoxaline-2-yl) propane] dihydrochlorides of 2 '-azo, 2,2 '-azo is two, and [2-(4,5,6,7-tetrahydrochysene-1H-1,3-diazepine-2-yl) propane] dihydrochloride, 2,2 '-azo is two, and [2-(3,4,5,6-tetrahydropyrimidine-2-yl) propane] dihydrochloride, 2, two [2-(the 5-hydroxyls-3 of 2 '-azo, 4,5,6-tetrahydropyrimidine-2-yl) propane] dihydrochloride, 2,2 '-azo two { 2-[1-(2-hydroxyethyl)-2-tetrahydroglyoxaline-2-yl] propane } dihydrochloride, 2,2 '-azo two [2-(2-tetrahydroglyoxaline-2-yl) propane], 2, two (2-methyl-N-phenyl third amidine) dihydrochlorides of 2 '-azo, 2, two [N-(4-the chloro-phenyl-)-2-methyl-prop amidine] dihydrochlorides of 2 '-azo, 2,2 '-azo [N-(4-hydroxyphenyl)-2-methyl-prop amidine] dihydrochloride, 2, two [2-methyl-N-(phenmethyl) third amidine] dihydrochlorides of 2 '-azo, 2, two [2-methyl-N-(2-propenyl) third amidine] dihydrochlorides of 2 '-azo, 2, two (the 2-methyl-prop amidine) dihydrochlorides of 2 '-azo, with 2, two [N-(2-the hydroxyethyl)-2-methyl-prop amidine] dihydrochlorides of 2 '-azo.Such azo-compound can use separately or wherein two or more uses that combine.

The add-on of radical initiator preferably, per 100 weight parts are the 0.001-20 weight part with the summation of general formula (2) or (3) one or more unsaturated compounds represented and the hydrosulphonyl silane compound of representing with general formula (4), more preferably being the 0.1-10 weight part, most preferably is the 0.1-5 weight part.

(temperature of reaction)

Hydrosulphonyl silane compound with general formula (4) expression is not particularly limited with the temperature that one or more unsaturated compounds of representing with general formula (2) or (3) react.But the preferred temperature of using for example is-50 ℃ to 200 ℃.Adopt the reasons are as follows of this temperature range.Temperature of reaction is lower than-50 ℃ and can causes the reactivity of these compounds greatly to reduce.On the other hand, the temperature of reaction that surpasses 200 ℃ can cause undue restriction can use solvent types, or is easy to occur side reaction.Therefore, temperature of reaction more preferably is 0-100 ℃, most preferably is 30-100 ℃.Have under the situation of unsaturated compound (for example vinylformic acid) as a kind of unsaturated compound of the present invention that high radically homo closes speed of reaction in use, the most preferred range of temperature of reaction is 30-70 ℃.When using the temperature of reaction of this scope, the equal polymerization reaction of unsaturated compound can be suppressed more effectively, also speed of response can be do not reduced.

(reaction times)

The reaction times limit depends on temperature of reaction and other factors.But, from this angle that concerns between reaction reliability and the productivity, preferably 0.5-100 hour usually reaction times, more preferably 1-24 hour.

(solvent)

In the reaction that the sulfhydryl compound of representing with general formula (4) and one or more unsaturated compounds of representing with general formula (2) or (3) carry out, solvent is preferably used for making these compounds to react evenly.The example of solvent comprises ethyl lactate, methylethylketone, pimelinketone, methyl-sulphoxide, ethylene glycol-single-butyl ether acetic ester, glycol ether, methyl propanediol, Pyranton, acetate methoxyl group propyl ester, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetic ester, 3-ethoxyl ethyl propionate, diglyme, N, N N,N-DIMETHYLACETAMIDE, 1,3-dimethyl-2-imidazolidone, 3-methoxypropionic acid methyl esters, 2-heptanone, toluene, tetrahydrofuran (THF), dioxane, chloroform, hexane, methyl alcohol and ethanol.These solvents can use separately or wherein two or more solvents be used in combination.The usage quantity of solvent preferably, per 100 weight parts are the 1-10000 weight part with the total amount of general formula (4) the hydrosulphonyl silane compound of representing and one or more unsaturated compounds of representing with general formula (2) or (3), more preferably 50-1000 weight part, most preferably 50-800 weight part.

(reaction atmosphere)

Hydrosulphonyl silane compound with general formula (4) expression has no particular limits with the atmosphere that one or more unsaturated compounds of representing with general formula (2) or (3) react.But, make the reaction system deoxidation preferably for example after reaction system drum nitrogen, or with ultrasonic wave after, these compounds carry out free radical reaction again.This is because when carrying out free radical reaction in atmosphere such as nitrogen, can suppress the disulphide that generates because of coupled reaction that sulfydryl carries out each other effectively.Although it is painted that the coupled reaction of sulfydryl usually causes, can prevent this reaction effectively, and can obtain the hydrolyzable silane compound of highly transparent.For reaction atmosphere, the problem of existence is that when having water in the reaction system, alkoxyl group is easy to spontaneous hydrolysis during this free radical reaction.Particularly when the hydrolyzable silane that contains carboxyl is subjected to free radical reaction, even exist a spot of water, alkoxyl group also to be easy to be hydrolyzed.It is therefore preferable that when using liquid starting material, use as molecular sieve, hydrolith or sal epsom dewatering agent and make this raw material dehydration, perhaps under nitrogen, distill in advance, randomly in the presence of these any dewatering agents, dewater.

As previously mentioned, hydrophilic polymer of the present invention is added to substrate surface, can makes the substrate surface highly-hydrophilic.Therefore, this polymkeric substance can be effectively applied to be applied to the coating of anti-fog coating and anti-external contamination especially in the various coating.

Second of the present invention is explained as follows.

(lithographic plate ground)

At first explain the hydrophilic layer that on carrier, forms; This layer is the feature of lithographic plate ground of the present invention.

Second hydrophilic layer contains solia particle according to the present invention, hydrophilic polymer and this solia particle surface chemistry bonding.Here, the chemical bonding on hydrophilic polymer and solia particle surface is also referred to as surface modification.

With the solia particle of hydrophilic polymer chemical bonding inorganic particles preferably.The example comprises metal oxide, as zinc oxide, titanium dioxide, ferric oxide and zirconium white, in the oxide containing silicon of visible region itself without any absorption, as silicic anhydride, calcium silicate hydrate and hydrated aluminium silicate (it also is known as white carbon(ink)) with as the clay mineral particulate of clay, talcum, kaolin and zeolite and so on.

Preferably 10 microns or littler of the median sizes of inorganic particles, 5 nanometers-5 micron more preferably, most preferably 10 nanometers-5 micron.Use is in the favourable part of the inorganic particles of this average particle size range, but not only can stably produce light-crosslinked particulate (this will describe afterwards), and can also allow these particulates remain adhered to satisfactorily on the carrier, also can satisfactorily they be retained near surface.

From wetting ability, film strength, carry out the difficulty or ease of surface modification with hydrophilic polymer, in the above inorganic particles of enumerating, oxide containing silicon is particularly preferred.Its specific examples comprises the ChemicalIndustries by Nissan, Snowtex ZL (particle diameter, 70-100 nanometer that Ltd. produces; 40% dioxide/silica gel liquid solution); Sylysia 350 (particle diameter, 3.5 microns) by Fuji SilysiaChemical Ltd. production; AEROSIL 130 (particle diameter, 160 nanometers by Nippon AerosilCo.Ltd. production; Silicon-dioxide); AEROSIL 200 (particle diameter, 16 nanometers by Nippon Aerosil Co.Ltd. production; Silicon-dioxide); With by Mizusawa IndustrialChemicals, Mizucasil P-527U (particle diameter, 60 nanometers that Ltd. produces; Silicon-dioxide).

In second of the present invention, hydrophilic polymer and solia particle surface chemistry bonding.The hydrophilic polymer that uses and be not subjected to special restriction with the bonding state of solia particle.Although following form (a) is common form, following grafting form (b) is preferred in the present invention, wherein, hydrophilic polymer chains terminal directly with fixing microparticle surfaces chemical bonding.

Form (a)

Form (b)

In grafting form (b), hydrophilic polymer is with mode similar to grafting and solia particle surface bond, and absorbs a large amount of water, to improve water retention capacity.Therefore, hydrophilic layer is a high-hydrophilic.And owing to carry out after the surface modification with hydrophilic polymer, the reactive group Y on the solia particle (for example OH yl) keeps exposed state on ground, microparticle surfaces top, and therefore by adding linking agent, it is possible making solia particle crosslinked mutually.Therefore, hydrophilic layer can have very high wetting ability, keeps outstanding film strength simultaneously.

Can be used for second of the present invention's not restriction especially of hydrophilic polymer.The example of the hydrophilic functional group that hydrophilic polymer has comprises carboxyl, sulfo group, sulfino, phosphono, amino and salt thereof, amide group, hydroxyl, ether and polyoxyethylene groups.

Use known technology rightly, available hydrophilic polymer carries out surface modification.For example, by sol gel reaction, can easily hydrophilic polymer be joined on the surface of silicon dioxide microparticle, this hydrophilic polymer has the structure that a kind of its polymer backbone has silane coupling end group.

Has the hydrophilic polymer that a kind of its polymer backbone has the hydrophilic polymer example of silane coupling end-group structure to comprise to explain among first of the present invention with chemical formula (1) expression.

The another kind of method of carrying out surface modification with hydrophilic polymer comprises with the silane coupling agent processing silica sphere with initiated polymerization ability, makes the hydrophilic monomer graft polymerization then.Therefore, can obtain the particulate that the hydrophilic polymer modification has been used on its surface.

Operable in the method hydrophilic monomer example comprises having carboxyl, sulfo group, the monomer of phosphate-based or amino and alkali, for example (methyl) vinylformic acid and an alkali metal salt thereof and amine salt, (methyl) vinylformic acid-2-hydroxyl ethyl ester, (methyl) acrylamide, N-monomethylol (methyl) acrylamide, N-dihydroxymethyl (methyl) acrylamide, allyl amine and halogen acid salt thereof, 3-vinyl propionic acid and an alkali metal salt thereof and amine salt, vinyl sulfonic acid and an alkali metal salt thereof and amine salt, (methyl) vinylformic acid-2-sulfo group vinyl acetate, (methyl) vinylformic acid-3-sulfo group propylene ester and an alkali metal salt and amine salt, single (methyl) vinylformic acid polyoxyethylene glycol ester, 2-acrylamido-2-methyl propane sulfonic acid and an alkali metal salt and amine salt, acid phosphorus oxygen polyoxyethylene glycol list (methyl) acrylate, and (methyl) vinylformic acid-2-trimethylammonium amino ethyl ester and halogen acid salt thereof.

Can carry out surface modification according to currently known methods, for example as Noboru Suzuki, Noboku Yuzawa, Atsushi Endo and Hiroshi Utsugi, Shikizai, 57, 429 (1984); Hiroshi Yoshioka andMasayuk í Ikeno, Hy  men, 21,33 (1983); Hiroshi Utsugi, Hy  men, 16,525 (1978); People such as K.Tanaka, Japanese Chemical Society meeting will (Bull.Chem.Soc.Jpn), 53, 1242 (1980); M.L.Hair and W.Hertl, physical chemistry magazine (J.Phys.Chem.), 77, 1965 (1973); People such as Ya.Davydov, chromatogram (Chromtographia), 14, 13 (1981); People such as K.Unger, colloidal polymer science (Colloid Polym.Sci.), 252, 317 (1974); R.Burwell and O.Leal, Chemical Society's magazine, chemistry circular (J.Chem.Soc.Chem.Commun.), 342 (1974); W.Stoeber, Kolloid-Z, 149, 39 (1956); People such as K.Yoshinaga, Polym.Adv.Technol., 3, 91 (1992); People such as N.Tsubokawa, polymkeric substance magazine (Polym.J.), 21, 475 (1989) and Franz.Pat.1368765DAS 1163784 or this paper patent and other file of quoting.

Spendable linking agent comprises the hydrolyzable polymerisable compound with following general formula (II) expression.

(R ^5′) _m-X-(OR ^6′) _4-m (II)

In formula (II), R ^{5 '}And R ^{6 '}Can be identical or different, each represents alkyl or aryl; X represents silicon, aluminium, titanium or zirconium atom, and m represents the integer of 0-2.R ^{5 '}Or R ^{6 '}When representing alkyl, it preferably has 1-4 carbon atom.Alkyl or aryl can have one or more substituting groups.With the compound of general formula (II) expression low-molecular weight compound preferably, its molecular weight be 1000 or below.

Hydrolyzable polymerisable aluminum contained compound example comprises aluminic acid trimethoxy ester, aluminic acid three ethoxy esters, aluminic acid 3 third oxygen esters and aluminic acid tetrem oxygen ester.The titanium-containing compound example comprises metatitanic acid trimethoxy ester, metatitanic acid four methoxyethoxy esters, metatitanic acid three ethoxy esters, metatitanic acid tetrem oxygen ester, metatitanic acid 4 third oxygen esters, metatitanic acid chlorine trimethoxy ester, metatitanic acid chlorine three ethoxy esters, metatitanic acid ethyl trimethoxy ester, metatitanic acid methyl three ethoxy esters, metatitanic acid ethyl three ethoxy esters, metatitanic acid diethyl diethoxy ester, metatitanic acid phenyl trimethoxy ester and metatitanic acid phenyl three ethoxy esters.The zirconium-containing compound example comprises and the corresponding zirconate of these titanic acid ester.

Hydrolyzable polymerisable silicon-containing compound example comprises Trimethoxy silane, triethoxyl silane, tripropoxy silane, tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane, methyltrimethoxy silane, ethyl triethoxysilane, propyl trimethoxy silicane, Union carbide A-162, ethyl triethoxysilane, propyl-triethoxysilicane, dimethyldimethoxysil,ne, the diethyl diethoxy silane, γ-chloropropyl triethoxysilane, γ-Qiu Jibingjisanjiayangjiguiwan, γ-sulfydryl propyl-triethoxysilicane, γ-An Jibingjisanyiyangjiguiwan, phenyltrimethoxysila,e, phenyl triethoxysilane, phenyl tripropoxy silane, xenyl dimethoxy silane and xenyl diethoxy silane.

The particularly preferred example of these compounds comprises tetramethoxy-silicane, tetraethoxysilane, methyltrimethoxy silane, ethyl trimethoxy silane, Union carbide A-162, ethyl triethoxysilane, dimethyldiethoxysilane, phenyltrimethoxysila,e, phenyl triethoxysilane, xenyl dimethoxy silane and xenyl diethoxy silane.

In second of the present invention, the particulate of surface modification can be one or both or multiple, can use separately with the compound of general formula (II) expression, or two or more are used in combination.Compound with general formula (II) expression can carry out partial hydrolysis, follows dehydrating condensation again.In order to improve the stability that image forming material stored with solution state before being applied to ground; the hydrolyzable polymeric organometallic compound that protection is effectively represented with general formula (II) is through the reactive metal hydroxyl of the inorganic polymer that partial hydrolysis and polymerization generated, for example silanol (Si-OH).More senior alcohol ester silanol (changing into Si-OR) (R is not meant specific group, and is meant some groups) with for example uncle-butanols or Virahol and so on can realize protecting silanol.For example, can higher alcohol be added to contain dispersion particulate silicon dioxide microparticle wherein inorganic mutually in, can realize this protection.Character according to inorganic phase adopts suitable method, and the water that for example adopts inorganic phase of heating and distillation to remove release makes inorganic phase dehydration, can further improve the stability in storage of this inorganic phase.Exist under the situation of example hydrochloric acid or ammonia and so on acid or alkali in mutually inorganic, this acid or alkali can play the hydrolytic polymerization catalyzer, and the concentration that reduces acid or alkali generally also is effective.With in acid or the alkali with the inorganic reduction that just is easy to realize its acid or alkali concn mutually.

In the present invention, in the hydrophilic layer of lithographic plate ground, the linking agent that can contain useful general formula (II) expression makes the crosslinked resulting surface modified particulate of the particulate/linking agent mixture of surface modification, and its amount generally is to count 2-90 weight % with hydrophilic layer all solids component.Preferably 5-80 weight % more preferably is 10-50 weight %.

Be lower than at fraction of particle under the situation of 2 weight %, hydrophilic layer does not have enough water retention capacities, so be easy to track down and recover stolen goods.When fraction of particle surpassed 50 weight %, not only hydrophilic layer intensity reduced, thereby caused the weather resistance of printing to reduce, and the sticking power between carrier and the hydrophilic layer also reduces.

[the generation method of surface modified particulate/linking agent mixture]

The organic/inorganic composite of the present invention that contains surface modified particulate/linking agent can prepare by hydrolytic-polymeric reaction.Any known method can both be used for this polyreaction.For example, can use the method for in Zoru-GeruH  No Kagaku (Agune Shofusha), describing.Preferred examples is as follows.Acid (for example phosphoric acid, hydrochloric acid, sulfuric acid or acetic acid), particularly preferably be phosphoric acid or hydrochloric acid, or alkali (for example ammoniacal liquor), be added in the alcoholic solution as catalyzer, preferably methyl alcohol or ethanolic soln, this solution contains surface-modified particulate of dispersion the present invention wherein and linking agent (for example using the compound of general formula (II) expression), prepares material solution.Then, this solution is at 0-100 ℃, 10-80 ℃ of following stirring and refluxing 5 minutes to 6 hours, particularly preferably is 10 minutes to 2 hours, so that cause hydrolytic-polymeric reaction preferably.Therefore, can generate the organic/inorganic composite material that contains surface modified particulate and linking agent.

Usually component is dissolved in the solvent, and with this solution coat on appropriate carriers, can make hydrophilic layer of the present invention.Solvent used herein has no particular limits.Examples of solvents comprises methylene dichloride, pimelinketone, methylethylketone, methyl alcohol, ethanol, propyl alcohol, ethylene glycol monomethyl ether, 1-methoxyl group-2-propyl alcohol, acetic acid-2-methoxyl group ethyl ester, acetic acid-1-methoxyl group-2-propyl ester, glycol dimethyl ether, methyl lactate, ethyl lactate, N, N-N,N-DIMETHYLACETAMIDE, N, dinethylformamide, tetramethyl-urea, N-Methyl pyrrolidone, methyl-sulphoxide, tetramethylene sulfone, gamma-butyrolactone, toluene and water.

These solvents can use separately or use with the mixture of two or more solvents.Component in solvent (all solids component that comprises additive) concentration is 1-50 weight % preferably.By the general 0.5-5.0 gram/rice preferably of coating and the dry amount (in solid) that on carrier, generates coating ²For coating, can adopt various technology.The example of coating technique comprises that wire bar applicator coating, rotary coating, spraying, curtain coating, dip-coating, air knife are coated with, blade coating and roller coat.

The thickness of hydrophilic layer of the present invention is 0.001-10 gram/rice preferably ², more preferably be 0.01-5 gram/rice ²The thickness of hydrophilic layer not only can have the present invention satisfactorily and give hydrophilic effect in this scope the time, and hydrophilic layer also has the sticking power with carrier satisfactorily, therefore can reach enough printing durabilities.

Although the carrier that uses in second of the present invention has no particular limits the flats carrier that it is preferably stable dimensionally.The carrier example comprises paper, plastic layer platen (polyethylene terephthalate for example, polyethylene, polypropylene or polystyrene), metal sheet (for example aluminium, zinc and copper), plastics film (for example Cellulose diacetate, cellulosetri-acetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, nitrocellulose, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate and polyvinylacetal), and adopt lamination or vapor deposition process to be coated with the paper or the plastics film of any metal in these metals.

The preferred vector that uses among the present invention is polyester film and aluminium sheet.They particularly preferably are polyester film in these carriers, because also can work to do above-mentioned carrier surface.

The preferred aluminium sheet that uses among the present invention comprises the Aluminium Alloy Plate of pure aluminum sheets and main ingredient aluminium and a small amount of one or more other elements.Also spendable is the plastics film that adopts lamination or vapor deposition process coating aluminium.The non-aluminium element example that contains in aluminium alloy comprises silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel and titanium.In the alloy, so non-aluminium element content is at the most up to 10 weight %.Although pure aluminum sheets is particularly preferred in the present invention, the aluminium sheet that contains a small amount of non-aluminium element also can use, because adopt existing refining techniques to be difficult to produce pure aluminium fully.As previously mentioned, the aluminium sheet that the present invention uses is not restricted on forming, and this aluminium sheet can suitably be selected from normally used known aluminium thin plate.It generally is about 0.1-0.6 millimeter that the present invention uses the thickness of aluminium sheet, and preferably the 0.15-0.4 millimeter more preferably is the 0.2-0.8 millimeter.

As previously mentioned, the present invention uses the preferably roughen of surface of carrier.Will be explained in last depression and the projection that forms in surface (solid surface) that the present invention uses carrier below.

[adjusting of surface depression and projection]

Bidimensional roughness parameter value is as follows.Center line average roughness R _aIt can be the 0.1-1 micron.Maximum height R _yIt can be the 1-10 micron.10 mean roughness R _zIt can be the 1-10 micron.

Mean distance S between depression and the projection _mIt can be the 5-80 micron.Local peak-to-peak mean distance S can be the 5-80 micron.Maximum height R _tIt can be the 1-10 micron.Medullary ray peak heights R _pIt can be the 1-10 micron.Medullary ray paddy degree of depth R _vIt can be the 1-10 micron.

These bidimensional roughness parameters are based on following definitions.

[center line average roughness R _a] select along centerline direction by roughness curve and to have the part of measuring length L.The arithmetical av of absolute value of the bias of getting this part medullary ray and roughness curve is as center line average roughness R _a

[maximum height R _y] select the part that has sl. along the average line direction by roughness curve.In the distance of roughness curve vertical direction measurement between this part crest line and valley line, and get its distance as maximum height R _y

[10 mean roughness] selected the part that has sl. along the average line direction by roughness curve.In this part, be base with the average line, at five climaxs of vertical direction height (Y _p) absolute value average, and be base with the average line, at the deep valley height (Y of five of vertical direction _v) absolute value average.Get 10 mean roughness of work in two mean value sums of micron.

[the mean distance S between depression and the projection _m] select the part that has sl. along the average line direction by roughness curve.In this part, measure corresponding to the average line of each peak, and amount to all these average lines with the paddy that is adjacent.In millimeter, the arithmetical av of these distances is got and is made mean distance S between many depressions and the projection _m

[local peak-to-peak mean distance S] selected the part that has sl. along the average line direction by roughness curve.In this part, measure length corresponding to the average line of every pair of adjacent local peaks.In millimeter, the arithmetical av of these distances is got and is made mean distance S between many local peaks.

[maximum height R _t] select part with sl. by roughness curve.So draw two straight lines parallel, so that this part is clipped between these straight lines with medullary ray.Article two, the distance between the straight line is got and is made maximum height R _t

[medullary ray peak heights R _p] select along centerline direction by roughness curve and to have the part of measuring length L.At medullary ray and be parallel to medullary ray and get and make medullary ray peak heights R by the distance between the straight line at this part climax _p

[medullary ray paddy degree of depth R _v] select along centerline direction by roughness curve and to have the part of measuring length L.At medullary ray and be parallel to medullary ray and get and make medullary ray paddy degree of depth R by the distance between the straight line of the deep valley of this part _v

(forming the type of depression and projection method)

Can adopt various technology to make solid surface coarse.For example, past solid surface sandblasts or uses as brush mechanical friction surface, forms depression with wear surface layer, thereby can form surfaceness.Can also adopt the method for mechanical embossing to form depression and projection.Can adopt intaglio printing etc. to form projection from the teeth outwards, thereby form surfaceness.Can use technology to form the layer that contains thin solia particle (matting agent), thereby form surfaceness at solid surface as coating or printing.Thin solia particle can add in (with additive) polymkeric substance in the stage of polymer formation film, thereby was formed with the polymeric film of depression and projection in its surface.In addition, carry out processing, can form surfaceness as solvent treatment, Corona discharge Treatment, Cement Composite Treated by Plasma, electron beam radiation treatment or x-ray irradiation processing and so on.Two or more technology in more such technology can be used in combination.Particularly preferably be adopt sandblast or technology that the resin printing forms surfaceness with form the technology of depression and projection by adding thin solia particle.

[thin solia particle method]

As thin solia particle, can use various materials, for example thin metal particle, fine metallic oxide particulate and organic or inorganic polymer or lower-molecular substance fine particles.The special example of fine particles comprises copper powder, glass putty, iron powder, oxide powder and zinc, silica powder, titanium oxide powder, aluminum oxide powder, molybdenum disulphide powder, Paris white, clay, mica, W-Gum, boron nitride, silicone resin particulate, polystyrene resin particulate, particulate fluorocarbon resin, acrylic resin particulate, vibrin particulate, acrylonitrile copolymer resin particle, Zinic stearas and mountain Yu acid calcium.Like this median size of fine particles preferably 0.05 micron or more than, more preferably be 0.1 micron or more than.Stick on the thin sheet surface or under the situation that forms the layer that contains fine particles on the thin sheet surface, the median size of fine particles is almost corresponding to the size of the surface depression that obtains with projection in fine particles.Under the situation of fine particles as additive adding thin plate, can be by the median size and the thick size of determining resultant surface depression and projection of thin plate of fine particles.Therefore, under one situation of back,, can determine the most suitable particle diameter that obtains best depression and projection size based on thin plate/fine particles composite test.

By comprising at the method example that forms depression and projection on this surface: before before film forming and by the composition that obtains, forming film, add the method for thin solia particle fixing thin solia particle on the matrix surface; Coating and dry thin solia particle is dispersed in make the fluidic method in the tackiness agent; By machinery pressurization thin solia particle is pressed into method in the film after the film forming; And after the film forming, with the method for thin solia particle galvanic deposit on film.

Before film forming, comprise following example with the special example that forms the method for refinement solia particle before the film by the composition that obtains.Contain PET masterbatch as the pigment of thin solia particle and melt extrude form film on drum cooler, this film at first stretches along machine direction, stretches along horizontal direction then, heat-treats at last.Therefore, obtained having the PET film of surface depression and projection.Pigment can be the pigment that contains one or more titanium oxide, aluminum oxide and silicon-dioxide.By regulating the amount of particle diameter and adding pigment, can regulate the medullary ray average surface roughness of film.For example, be about 0.5-5 weight % by selecting particle diameter for the pigment and the selection adding amount of pigment of about 1-10 micron, can regulate roughness.Pigment particle size is big more, and amount of pigment is high more, and the medullary ray average surface roughness increases just big more.In order to reach desired surface depression and projection, the essential add-on of selecting pigment particle size and regulating pigment.

(method sandblasts)

Sandblasting is to allow the small grain size abrasive material invest the polymeric film surface with high speed, thereby makes the technology of film surface roughen.This processing of sandblasting can adopt currently known methods to implement.For example, silicon carbide (alpha-silicon nitride powders), metal particle etc. force with pressurized air and blow to film surface, and this processing can be realized like this in washing and dry film surface again.The medullary ray average surface roughness that employing is sandblasted and formed on film surface can be adjusted by the amount of abrasive (frequency of per unit area) of regulating the particle diameter blown particulate and use when handling.Particle diameter is big more and amount of abrasive is big more, and then the medullary ray average surface roughness of film surface is just high more.

More particularly, handling owing to sandblasting is that abrasive material blows to film surface with pressurized air and handles this surface, and so depression that forms and projection can be regulated by the control treatment condition that sandblast.

Blow to the processing of film from the mouth that sandblasts at abrasive material, the treatment condition that should regulate comprise amount of abrasive to be blown (amount of sandblasting), angle (angle sandblasts) between mouth and the film and the distance (distance sandblasts) between mouth and the film of sandblasting sandblast.Abrasive material in the hopper ejects from the mouth that sandblasts by the pressurized air of being sent here by air vessel, blows to film surface, thereby under optimal conditions is sandblasted in the surface.For example in the open No.34866/1996,90827/1999 and 254590/1999 of Japanese Patent, this method was described as known technology.

When sandblasting, necessary is to select treatment condition, so that be that abrasive material or the abrasion dust that generates all do not stay after processing, film strength does not reduce yet.Such treatment condition can suitably be determined by test.

Such treatment condition example comprises following condition.Use silica sand or other abrasive material as abrasive material.But, preferably use preferably 0.05-10 millimeter of particle diameter, more preferably be the silica sand of 0.1-1 millimeter.Preferably 100-300 millimeter of the distance that sandblasts.The angle that sandblasts is the 45-90 degree preferably, more preferably is the 45-60 degree.In addition, the amount of sandblasting 1-10 thousand Grams Per Minutes preferably.These conditions not only can prevent to stay on the polymer surfaces in the abrasion dust of sandblast back abrasive material or generation, but also are suitable for controlling the degree of depth of removing layer by wearing and tearing.Wearing depth is preferably adjusted to great majority and is the 0.01-0.1 micron, thereby can prevent that film strength from reducing.

In the present invention, between carrier and hydrophilic layer, form undercoat.Preferred undercoat is the undercoat that contains hydrophile adhesive mass and silicon-dioxide among the present invention.

As the hydrophile adhesive mass in the undercoat, can use albumen, preferably gelatinum usually.But gelatinum can partly or entirely be used synthetic, and semisynthetic or natural polymkeric substance replaces.The synthetic substitute of gelatinum comprises polyvinyl alcohol, poly-(N-vinyl pyrrolidone), polyvinyl imidazol, polyvinyl pyrazoles, polyacrylamide, polyacrylic acid and their derivative, particularly their multipolymer.The natural substitute for example of gelatinum comprises other albumen, for example zein, albumin and casein, Mierocrystalline cellulose, sugar, starch and alginate.The semi-synthetic substitute example of gelatinum usually comprises the natural product of modification.Their special example comprises the gelatinum derivative that adopts following method to obtain: with the gelatinum of alkylating agent or acylation agent modification; or gelatinum grafting polymerisable monomer and derivatived cellulose, for example hydroxy alkyl cellulose, carboxymethyl cellulose, phthaloyl Mierocrystalline cellulose and sulfate cellulose.

The preferably anionic silicon-dioxide of the silicon-dioxide that in undercoat, contains.Preferably at least 100 meters of the surface-area of colloid silica ²/ gram more preferably is at least 300 meters ²/ gram.

Employing is by S.Brunauer, and P.H.Emmett and E.Teller are in U.S. chemical institute magazine, and the 60th rolls up (1938), and the BET method that proposes in the 309-312 page or leaf is measured the surface-area of colloid silica.

Silica dispersions can contain other material, for example as aluminium salt, stablizer and sterilant.

This class silicon-dioxide can buy, and its commodity KIESELSOL 100, KIESELSOL300 by name and KIESELSOL 500 (" KIESELSOL " is in Germany, Leverkusen, and the registered trade mark of Farbenfabriken BayerAG, each numeral is with rice ²/ restrain surface-area) into unit.

Hydrophile adhesive mass weight and silica weight are than preferably being lower than 1 in the undercoat.Although should be than lower limit be not too important, preferably 0.2 or bigger.The weight ratio of hydrophile adhesive mass and silicon-dioxide more preferably is 0.25-0.5.

The amount that generates undercoat is preferably greater than 200 milligrams/meter ², less than 750 milligrams/meter ², more preferably be 250-500 milligram/rice ²

As required, preferably be coated with by moisture colloidal dispersion and above-mentioned bottom coating composition under the tensio-active agent existence.

[explanation of imaging layer]

(photoactive layer or heat-sensitive layer)

On hydrophilic layer of the present invention, form imaging layer (photoactive layer or heat-sensitive layer).This imaging layer comprises positive photosensitive composition or negative photosensitive composition.

(positive photosensitive composition)

Following known positive photosensitive composition ((a) and (b)) is fit to the present invention to be used.

(a) common positive photosensitive composition, it contains naphthoquinones two nitrine and novolac resin.

(b) chemical enhancement type positive photosensitive composition, it contains the alkali of useful acid-decomposition radical protection-dissolve compound and gives birth to the combination of sour agent.

These compositions (a) and (b) knowing in the art.But, preferredly be to use these compositions and any following positive photosensitive composition (any combination in the combination of (c)-(f).

(c) the positive composition of describing in the open No.282672/1998 of Japanese Patent of laser-sensitization, it contains sulphonate polymkeric substance and infrared absorbing agents, can produce the lithographic plate that need not any colour developing by said composition.

(d) the positive composition of describing in EP 652483 and the open No.502260/1994 of Japanese Patent of laser-sensitization, it contains carboxylate polymer and any gives birth to sour agent or infrared absorbing agents, can produce the lithographic plate that need not any colour developing by said composition.

(e) the positive composition of in the open No.095421/1999 of Japanese Patent, describing of laser-sensitization, it contains alkali-dissolve compound and heat decomposable material, it at undecomposed state mainly as reducing alkali-the dissolve solubleness of compound.

(f) alkalescence that contains infrared absorbing agents, novolac resin and the decomposing inhibitor positive photosensitive composition that develops the color can be produced the positive lithographic plate of alkaline colour developing type by this composition.

Some compounds that in positive photosensitive composition ((a)-(f)), use of explained later.

" give birth to sour agent "

The sour agent of life that can use in positive photosensitive composition is by heat or the acidic compound of light action.The general sour agent example of such life that uses comprises light trigger, the light trigger of radical photopolymerization effect, dyestuff the light discoloring agent or the phototropic agent of cationic photopolymerization effect; under rayed, produce acid and be used for for example known compound of little protective layer, and their mixture.One or more give birth to sour agent can suitably be selected from these living sour agent and uses.

The particular instance of giving birth to sour agent comprises father-in-law's salt, as at S.I.Schlesinger, and Photogr.Sci.Eng., 18,387 (1974) and people such as T.S.Bal, polymkeric substance, diazonium father-in-law's salt of descriptions in 21,423 (1980); In US 4 069055 and 4 069 056, the ammonium salt of describing among the open No.140 140/1991 of Japanese Patent; In people such as D.C Necker, macromole (Macromolecules), 17,2468 (1984), people such as C.S.Wen, Teh, Proc.Conf.Rad.Curing ASIA, the 478th page, Tokyo, the phosphorus father-in-law salt of describing in October (1988) and US 4 069 055 and 4 069 056; People such as J.V.Crivello, macromole, 10 (6), 1307 (1977), chemistry and engineering, news (Chem.﹠amp; Eng.New), November, 28 days, the 31st page (1988), European patent 104 143, US 339 049 and 410 201 and the open No.150 848/1990 and 296 514/1990 of Japanese Patent in the iodonium salt described; People such as J.V.Crivello, polymkeric substance magazine, 17,73 (1985), people such as J.V.Crivello, organic chemistry magazine, 43,3055 (1987), people such as W.R.Watt, the polymer science magazine, polymer chemistry version (J.Polymer Sci., Polymer Chem.Ed.) 22,1789 (1984), people such as J.V.Crivello, polymkeric substance communique, 14,279 (1985), people such as J.V.Crivello, macromole, 14 (5) 1141 (1981), people such as J.V.Crivello, the polymer science magazine, polymer chemistry version, 17,2877 (1979), European patent 370693, US 3 902 114, European patent 233 567,297 443 and 297 442; US 4 933 377,410201,339 049,4 760 013,4 734 444 and 2 833 827 and German Patent 2 904 626,3 604580 and 3 604 581 in the sulphur father-in-law salt described; People such as J.V.Crivello, macromole, 10 (6) 1307 (1977) and people such as J.V.Crivello, the polymer science magazine, the polymer chemistry version, 17,1047 (1979) the middle selenium salt of describing, and people such as C.S.Wen, Teh, Proc.Conf.Rad.Curing ASIA, the 478th page, Tokyo, the arsenic salt of describing in October (1988).Give birth to sour agent example and also be included in US 3 905 815; The organohalogen compound of describing among the open No.36281/1973,32070/1980,239736/1985,169835/1986,169837/1986,58241/1987,212401/1987,70243/1988 and 298339/1988 of Japanese patent laid-open publication gazette No.4605/1971 and Japanese Patent; People such as K.Meier, J.Rad.Curing, 13 (4), 26 (1986), people such as T.P.Gill, inorganic chemistry, 19,3007 (1980), D.Astruc, Acc.Chem.Res., 19 (12), 377 (1896) and the open No.161445/1990 of Japanese Patent in organometallic compound/Organohalogen compounds combination of describing.People such as S.Hayase, polymer science magazine, 25; 753 (1987), people such as E.Reichman, polymer science magazine; the polymer chemistry version, 23,1 (1985); people such as Q.Q.Zhu, photochemistry magazine (J.Photochem.), 36; 85,39,317 (1987); people such as B.Amit, tetrahedron communication (Tetrahedron Lett.) (24) 2205 (1973), people such as D.H.R.Barton; Chemical Society's magazine, 3571 (1965), people such as P.M.Collins; Chemical Society's magazine; Perkin I, 1695 (1975), people such as M.Rudinstein; the tetrahedron communication; (17), 1445 (1975), people such as J.W.Walker; U.S. chemical institute magazine; 110,7170 (1988), people such as S.C.Busman; imaging technique magazine (J.Imaging Technol.); 11 (4), (1985), people such as H.M.Houlihan; macromole; 21,2001 (1988), people such as P.M.Collins; Chemical Society's magazine; chemical communication, 532 (1972), people such as S.Hayase; macromole; 18,1799 (1985), people such as E.Reichmanis; ECS's magazine; solid-state science and technology (J.Electrochem.Soc., SolidState Sci.Technol.), 130 (6); people such as F.M.Houlihan; macromole, 21,2001 (1988); European patent 0 290 750; 046 083; 156 535; 271 851 and 0 388 343, US 3 901 710 and 4 181531 and Japanese Patent the light with neighbour-nitrobenzyl base class blocking group-Sheng acid agent of describing is disclosed in 198538/1985 and 133022/1978.People such as Tunooka, polymkeric substance is preprinted, and Japan (Polymer Preprints, Japan), 35 (8), people such as G.Bemer, J.Rad.Curing, 13 (4), people such as W.J.Mijs, application techniques (Coating Technol.), 55 (697), 45 (1983), Akzo, people such as H.Adachi, polymkeric substance is preprinted, Japan, 37 (3), European patent 0 199 672,84 515,199 672,044 115 and 0 101 122, US4 618 554,4 371 605 and 4 431 774, and the open No.18143/1989 of Japanese Patent, the compound that the photodissociation of describing in 245756/1990 and 140109/1991 produces sulfonic acid and represents with imino-sulphonate etc.Two sulphones of in the open No.166544/1986 of Japanese Patent, describing.

In addition, can use and to give birth to sour agent and add polymer backbone or the resulting compound of side chain.This polymerizable compound example provides in following document: people such as M.E.Woodhouse for example, U.S. chemical institute magazine, 104,5586 (1982), people such as S.P.Pappas, imaging science magazine, 30 (5), 218 (1986), people such as S.Kondo, Makromol.Chem., Rapid Commun., 9,625 (1988), people such as Y.Yamada, Makromol.Chem., 152,153,163 (1972), people such as J.V.Crivello, the polymer science magazine, the polymer chemistry version, 17,3845 (1979), US 3 849 137, the open No.26653/1988 of German Patent 3 914 407 and Japanese Patent, 164824/1980,69263/1987,14603/1988,163452/1988,153853/1987 and 146029/1988.

Also can use acidic compound under light action, its document is as follows: V.N.R.Pillai, and synthetic, (1), 1 (1980), people such as A.Abad, tetrahedron communication, (47) 4555 (1971), people such as D.H.R.Barton, Chemical Society's magazine, (C), 329 (1970), US 3 779 778 and European patent 126 712.

The amount of the sour agent of life that adds among the present invention generally is to count about 0.001-40 weight % with photoactive layer or heat-sensitive layer all solids component, and preferably 0.01-20 weight % more preferably is 0.1-5 weight %.

" alkali-dissolve compound "

The alkali that can use in positive photosensitive composition-dissolve compound is, reduces alkali solubility in the presence of decomposing inhibitor, and when decomposing inhibitor decomposes the alkali of recovery alkali solubility-dissolve compound.

The alkali that uses in positive photosensitive composition-dissolve the compound example comprises novolac resin, poly-(hydroxy styrenes) and acrylic resin.

Spendable in the present invention novolac resin is phenol and the resulting resin of aldehyde condensation under acidic conditions.Preferred novolac resin example comprises, the novolac resin that obtains by phenol and formaldehyde, by-novolac resin that cresols and formaldehyde obtain, the novolac resin that obtains by p-Cresol and formaldehyde, the novolac resin that obtains by neighbour-cresols and formaldehyde, the novolac resin that obtains by octyl phenol and formaldehyde, by-novolac resin that cresols and p-Cresol and formaldehyde obtain, and by phenol and one or more cresols (adjacent-, between-, p-Cresol or any between-and p-Cresol mixture, between-and neighbour-cresols mixture, and adjacent-and the p-Cresol mixture) mixture and the novolac resin that obtains of formaldehyde.These novolac resin weight-average molecular weight are 800-200 000 preferably, and number-average molecular weight is 400-60 000.

Except novolac resin, spendable alkali in positive photosensitive composition-dissolve compound example comprises poly-(hydroxy styrenes), hydroxy styrenes/N-substituted maleimide amine copolymer thing, hydroxy styrenes/copolymer-maleic anhydride, the urethane polymer that has the acrylate copolymer of alkali-molten group and have alkali-molten group.Alkali-molten group example comprises carboxyl, phenolic hydroxyl group, sulfo group, phosphono and imide.

Under the situation of the hydroxystyrene polymers that uses for example poly-(right-hydroxy styrenes), poly-(-hydroxy styrenes), right-hydroxy styrenes/N-substituted maleimide amine copolymer thing or right-hydroxy styrenes/copolymer-maleic anhydride and so on, their weight-average molecular weight is 2000-500 000 preferably, more preferably is 4000-300000.

Acrylate copolymer example with alkali-molten group comprises methacrylic acid/benzyl methacrylate multipolymer, poly-(hydroxy phenyl Methacrylamide), poly-(crylic acid hydroxylphenyl base carbonyl acyloxy ethyl ester), poly-(vinylformic acid 2,4-dihydroxy phenyl carbonyl acyloxy ethyl ester) and alkali-molten acrylate copolymer of describing in the open No.211731/1996 of Japanese Patent.The weight-average molecular weight of these acrylate copolymer is 2000-500 000 preferably, more preferably is 4000-300 000.

Urethane polymer example with alkali-molten group comprises xenyl methane diisocyanate and hexamethylene diisocyanate and Tetraglycol 99 and 2, and two (methylol) propionic acid of 2-react resulting resin.

From the angle of developing ability, preferably have the hydroxystyrene polymers and the acrylic copolymer of alkali-molten group in these alkali-insoluble polymer may.

The alkali of Shi Yonging-dissolve compound is by acid-separate radical protection in the present invention.Acid-separate the group example and comprise ester group and carbamate groups.

In light sensation photosphere of the present invention or hotness photosphere, these alkali-dissolve the content of compound in this layer all solids component, generally are about 10-90 weight %, and preferably 20-85 weight % more preferably is 30-80 weight %.Content at alkali-dissolve compound is lower than under the situation of 10 weight %, and the weather resistance of light sensation photosphere or hotness photosphere is weakened.On the other hand, to be higher than 90 weight % all be undesirable from susceptibility and weather resistance two aspects to the content of alkali-dissolve compound.

Compound can use separately or two or more are used in combination for these alkali-dissolve.

" decomposing inhibitor "

The decomposing inhibitor that can use in positive photosensitive composition is can resolve into the molten compound of alkali by the acid effect.The decomposing inhibitor example comprises carboxylic acid and phenolic compound, and their adopt the chemical reinforcing type acid use in the protective layer field-separate group protected, for example uncle-butyl ester, carboxylamine uncle-butyl ester and alkoxyalkyl methacrylate.

In light sensation photosphere of the present invention or hotness photosphere, the content of decomposing inhibitor in this layer all solids component, generally is about 5-90 weight %, preferably 10-80 weight %.

Preferred quinonediazide compound comprises o-quinone two triazo-compounds.

Operable in the present invention o-quinone two triazo-compounds are the compounds with various structures of at least one o-quinone diazido group, and are used for improving when thermolysis alkali-solubleness.Just, when thermolysis, the o-quinone diazide not only loses the ability that inhibition alkali-dissolve compound decomposes, and also loses the ability that itself becomes alkali-molten material.Based on these two kinds of effects, the o-quinone diazide helps photoactive substance to decompose.The o-quinone two triazo-compound examples that can use in the present invention are at J.Kosar, optical sensing system (Ligh-sensitive systems), 339-352 page or leaf (John Wiley ﹠amp; Sons Inc.) provides.But, be particularly preferred by reacting the o-quinone diazide sulphonate or the sulphonamide that obtain with various aromatics polyols or aromatic amido compound.Benzoquinones-(1,2)-two nitrine SULPHURYL CHLORIDE or naphthoquinones-(1,2)-ester of two nitrine-5-SULPHURYL CHLORIDE and pyrogallol-acetone resin also is preferred, those compounds of for example in Japanese patent laid-open publication gazette No.28403/1968, describing, and benzoquinones-(1,2)-two the ester of nitrine SULPHURYL CHLORIDE or naphthoquinones-(1,2)-two nitrine-5-SULPHURYL CHLORIDE and resinox also is preferred, and they were described in US 3 046 120 and 3 188210.

In addition, the ester of naphthoquinones-(1,2)-two nitrine-4-SULPHURYL CHLORIDE and resinox or cresol-formaldehyde resin, and the ester of naphthoquinones-(1,2)-two nitrine-4-SULPHURYL CHLORIDE and pyrogallol-acetone resin also is preferred.Other useful o-quinone two triazo-compounds are known, report in many patent documents.Their example was described in following document: the open No.5303/1972,63802/1973,63803/1973,96575/1973,38701/1974 and 13354/1973 of Japanese Patent, Japanese patent laid-open publication gazette No.11222/1966,9610/1970 and 17481/1974, US 2 797 213,3 454 400,3 544 323,3 573 917,3 674 495 and 3 785825, English Patent 1 227 602,1 251 345,1 267 005,1 329 888 and 1 330 932, and German Patent 854 890.

The content of o-quinone two triazo-compounds in photoactive layer of the present invention or heat-sensitive layer in this layer all solids component, generally is about 1-50 weight %, and preferably 5-30 weight % more preferably is 10-30 weight %.These compounds can use separately or use with the mixture of two or more these compounds.Be lower than under the situation of 1 weight % at o-quinone two triazo-compound content, as-record character is impaired.On the other hand, o-quinone two triazo-compound content surpass 50 weight % and cause picture district weather resistance variation, and sensitivity is variation also.

In photoactive layer of the present invention or heat-sensitive layer, the decomposition except that o-quinone two triazo-compounds suppresses compounds content, in this layer all solids component, generally is about 1-50 weight %, and preferably 5-30 weight % more preferably is 10-30 weight %.

(negative photosensitive composition)

Can use following known negative photosensitive composition ((g)-(i)) in the present invention.

(g) negative photosensitive composition, it contains the polymkeric substance with Photocrosslinkable group and triazo-compound.

(h) the negative photosensitive composition of describing in the open No.101651/1984 of Japanese Patent, it contains diazonium compound.

(i) the negative photosensitive composition of the photopolymerization of describing in US 262 276 and the open No.63054/1990 of Japanese Patent, it contains Photoepolymerizationinitiater initiater and adduction-polymeric non-saturated compounds.

(j) the negative photosensitive composition of describing in the open No.095421/1999 of Japanese Patent, it contains alkali-dissolve compound, give birth to sour agent and acid-cross-linking compounds.

The compound that uses in negative photosensitive composition ((g)-(j)) is explained as follows.

" polymkeric substance " with photo-crosslinking group

The polymkeric substance with photo-crosslinking group that can use in negative photosensitive composition, preferably a kind of have a polymkeric substance that aqueous alkalescence colour developing liquid is had the photo-crosslinking group of avidity.These examples of polymer are included in the polymkeric substance of describing among the US 5 064 747, and it has the group of Photocrosslinkable on molecular backbone chain or side chain, for example-and CH=CH-CO-; The multipolymer of in the open No.15711/1979 of Japanese Patent, describing, it has laurate group and carboxyl; The vibrin of in the open No.165646/1985 of Japanese Patent, describing, it has benzene dicarboxylic acid residue and carboxyl; The vibrin of in the open No.203630/1985 of Japanese Patent, describing, it has benzene dicarboxylic acid residue and phenolic hydroxyl group; The vibrin of in the open No.42858/1982 of Japanese Patent, describing, it has benzene dicarboxylic acid residue and sodium imino-diacetic alkylsulfonyl, and the polymkeric substance of describing in the open No.208552/1984 of Japanese Patent, and it has azido-and carboxyl on side chain.

In photoactive layer of the present invention or heat-sensitive layer, have the content of the polymkeric substance of photo-crosslinking group, in this layer all solids component, generally be about 5-100 weight %, preferably 10-95 weight % more preferably is 20-90 weight %.

" triazo-compound "

The triazo-compound example that can use in negative photosensitive composition comprises 2, two (4-triazobenzene the methylene radical)-4-methylcyclohexanes and 4,4 of 6-'-diazido xenyl sulphur.

In photoactive layer of the present invention or heat-sensitive layer, the content of triazo-compound in this layer all solids component, generally is about 5-95 weight %, and preferably 10-90 weight % more preferably is 20-80 weight %.

" alkali-dissolve compound "

The alkali that uses in the alkali that can use in negative photosensitive composition-dissolve compound and the photosensitive composition just-dissolve compound is identical.

" diazonium compound "

The diazo resin example that can use in negative photosensitive composition comprises with diazo diarylamine and the represented diazo resin of active carbonyl compound condensation salt.Preferably insoluble in water, and in organic solvent soluble photosensitive azo resin.

So the special preferred embodiment of azo resin comprise 4-diazo p-diaminodiphenyl, 4-diazo 3-methyl diphenyl amine, 4-diazo-4 '-methyl diphenyl amine, 4-diazo-3 '-methyl diphenyl amine, 4-diazo-4 '-methoxyl biphenyl amine, 4-diazo-3-methyl 4 '-ethoxybenzidine or 4-diazo-3-methoxyl biphenyl amine and formaldehyde, Paraformaldehyde 96, acetaldehyde, phenyl aldehyde, 4,4 '-organic acid salt or the inorganic acid salt of the condensation product of bi-methoxy methyl diphenyl ether.

The organic acid example comprises methylsulfonic acid, Phenylsulfonic acid, toluenesulphonic acids, xylene monosulfonic acid, 1,3,5 tri-methyl p-toluenesulfonates, Witco 1298 Soft Acid, naphthene sulfonic acid, propyl group naphthene sulfonic acid, 1-naphthol-5-sulfonic acid, 2-nitrobenzene-sulfonic acid, 3-chlorobenzenesulfonic acid and 2-hydroxyl-4-anisole ketone 5-sulfonic acid.

The mineral acid example comprises phosphofluoric acid, Tetrafluoroboric acid and sulfocyanic acid.

Other spendable diazonium compound example is included in the azo resin of describing among the open No.30121/1979 of Japanese Patent, and wherein main chain is a polyester chain; The diazo resin of in the open No.273538/1986 of Japanese Patent, describing, it is to react resulting resin by polymkeric substance with carboxylic anhydride residue and the diazonium compound with hydroxyl; And react resulting diazo resin by polyisocyanate compounds and the diazonium compound with hydroxyl.

The content of nitrine resin in photoactive layer of the present invention or heat-sensitive layer is in this layer all solids component, preferably 0-40 weight %.As required, two or more diazo resins can be used in combination.

" Photoepolymerizationinitiater initiater and adduction-polymerization non-saturated compounds "

Adduction-polymerization the non-saturated compounds and the Photoepolymerizationinitiater initiater example that can use in negative photosensitive composition comprise, US 2 760 863 and 3 060 023 and Japanese Patent open No.121448/1987 in describe, adduction-polymerization non-saturated compounds with two or more ethylidene end groups, and the Photoepolymerizationinitiater initiater of describing herein.

The content of adduction in photoactive layer of the present invention or heat-sensitive layer-polymerization non-saturated compounds in this layer all solids component, generally is 5-95 weight %, preferably 5-80 weight %.The content of Photoepolymerizationinitiater initiater in photoactive layer or heat-sensitive layer in this layer all solids component, generally is 1-80 weight %, preferably 5-50 weight %.

" give birth to sour agent "

The sour agent of using in the sour agent of life that can use in negative photosensitive composition and the photosensitive composition just of life is identical.

" acid-cross-linking compounds "

Acid-the cross-linking compounds that can use in negative photosensitive composition is meant compound crosslinked in the presence of acid.Acid-cross-linking compounds example comprises aromatics and the heterogeneous ring compound that replaces with two or more groups that are selected from methylol, acetoxyl methyl and alkoxy methyl.Preferably use phenol and the aldehyde resulting compound of condensation under alkaline condition in these compounds.

The preferred embodiment of compound comprises as noted above usefulness phenol and formaldehyde resulting compound of condensation under alkaline condition like this, similarly by-compound that cresols and formaldehyde obtain, the compound that similarly obtains, similarly by 4 by connection phenol A and formaldehyde, 4 '-compound that Lian phenol and formaldehyde obtain, and in GB 2 082 339 with the disclosed compound of resol resin.

The weight-average molecular weight of these acid-cross-linking compounds is 500-100 000 preferably, and number-average molecular weight is 200-50 000.

The preferred embodiment of other acid-cross-linking compounds is included in the disclosed aromatic substance that replaces with alkoxy methyl or oxiranylmethyl radical among the EP-A-0 212 482; The condenses and the urea-formaldehyde condensation products of the trimeric cyanamide of disclosed monomer or oligopolymer and formaldehyde in EP-A-0 133 216, DE-A-3 634 671 and DE 3 711 264, and the compound of disclosed alkoxyl group-replacement in EP-A-0 212 482.

Other preferred embodiment comprises the derivative of trimeric cyanamide and formaldehyde in addition, and it has at least two free N-methylols, N-alkoxy methyl or N-acyloxy methyl.Particularly preferably be N-(alkoxymethyl)-2 radical derivative in these compounds.

The silanol of low-molecule or oligomerization can be used as siliceous linking agent.Their example comprises dimethyl-and xenyl silandiol, and has carried out preliminary condensation and contained the oligopolymer of any of these silanol units.For example can use disclosed oligopolymer in EP-A-0 377 155.

To illustrate in greater detail the present invention by following embodiment.

Embodiment 1 (synthesizing of polymer compound 1)

In 500 milliliters of three-necked bottles, add 50 gram acrylamides, 3.4 gram sulfydryl propyl trimethoxy silicanes and 220 gram dimethyl formamides.Under 65 ℃ of nitrogen gas stream, toward wherein adding 0.5 gram 2,2-azo two (2, the 4-methyl pentane nitrile).The mixture that obtains under agitation keeps this temperature to reach 6 hours, and then cool to room temperature is poured 2 liters of vinyl acetic monomers then into.As a result, separate out solid.This solid is weighed as 52.4 grams after drying.GPC shows that this solid is that weight-average molecular weight is the polymkeric substance of 3000 (calculating with polystyrene standard), ¹³C-NMR composes (DMSO-d ₆) show that this polymkeric substance has the trimethoxysilyl (50.0ppm) that adds its end.

Embodiment 2 (polymer compound 2-9's is synthetic)

With as polymer compound 1 same way as synthesized polymer compounds 2-9, only be to use corresponding monomer to replace acrylamide.By ¹³The C-NMR spectrum determines that synthetic polymer compound like this is each polymkeric substance that all adds trimethoxysilyl at its end.In table 1, list the polymer compound weight-average molecular weight (calculating) that adopts gpc measurement with polystyrene standard.

Table 1

Polymer compound	Weight-average molecular weight
Polymer compound	Weight-average molecular weight	2	4500
3	3300	2	4500
3	3300	4	4200
5	5600	4	4200
5	5600	6	6800
7	2200	6	6800
7	2200	8	3300
9	1900	8	3300

Embodiment 3 (synthesizing of polymer compound 10)

In 500 milliliters of three-necked bottles, add 50 gram acrylamides, 3.1 gram mercapto methyl methyldiethoxysilane and 212 gram dimethyl formamides.Under 65 ℃ of nitrogen gas stream, toward wherein adding 0.5 gram 2,2-azo two (2, the 4-methyl pentane nitrile).The mixture that obtains under agitation keeps this temperature to reach 6 hours, and then cool to room temperature is poured 2 liters of vinyl acetic monomers then into.As a result, separate out solid.This solid is weighed as 50.5 grams after drying.GPC shows that this solid is that weight-average molecular weight is the polymkeric substance of 2500 (calculating with polystyrene standard), ¹³C-NMR composes (DMSO-d ₆) show that this polymkeric substance has the methyl diethoxy silyl (58.3ppm) that adds its end.

Embodiment 4 (synthesizing of polymer compound 11)

In 500 milliliters of three-necked bottles, add 50 gram vinylformic acid, 3.1 gram sulfydryl propyl group methyl dimethoxysilanes and 212 gram dimethyl formamides.Under 65 ℃ of nitrogen gas stream, toward wherein adding 0.5 gram 2,2-azo two (2, the 4-methyl pentane nitrile).The mixture that obtains under agitation keeps this temperature to reach 6 hours, and then cool to room temperature is poured 2 liters of vinyl acetic monomers then into.As a result, separate out solid.This solid is weighed as 49.5 grams after drying.GPC shows that this solid is that weight-average molecular weight is the polymkeric substance of 2700 (calculating with polystyrene standard), ¹³C-NMR composes (DMSO-d ₆) show that this polymkeric substance has the methyl dimethoxy oxygen base silyl (50.0ppm) that adds its end.

Embodiment 5 (polymer compound 12-17's is synthetic)

With as polymer compound 1 same way as synthesized polymer compounds 12-17, only be to use corresponding monomer to replace acrylamide, use methyl alcohol and 2,2 '-two (isopropylformic acid) dimethyl esters of azo, replace respectively dimethyl formamide and 2,2 '-azo two (2, the 4-methyl pentane nitrile).By ¹³The C-NMR spectrum determines that each all is the polymkeric substance that adds trimethoxysilyl (50.0ppm) at its end for these synthetic polymer compounds.In table 2, list these polymkeric substance weight-average molecular weight (calculating) that adopt gpc measurement with polystyrene standard.

Table 2

Polymer compound	Weight-average molecular weight
Polymer compound	Weight-average molecular weight	12	9000
13	11000	12	9000
13	11000	14	10000
15	8000	14	10000
15	8000	16	9000
17	11000	16	9000

Embodiment 6 (synthesizing of polymer compound 18)

In 500 milliliters of three-necked bottles, add 135 gram methyl alcohol.Under 60 ℃ of nitrogen gas stream, in 2 hours toward wherein little by little Dropwise 50 gram acrylamide, 8.7 gram N-vinyl pyrrolidones, 7.7 gram sulfydryl propyl trimethoxy silicanes, 0.54 gram 2,2 '-two (isopropylformic acid) dimethyl esters of azo and 135 gram methyl alcohol.After being added dropwise to complete.The mixture that obtains under agitation keeps this temperature to reach 4 hours, and then cool to room temperature is poured 2 liters of acetone into, then to be settled out solid.This solid separates after filtration, carries out drying again.Solid is weighed as 60.5 grams after drying.GPC shows that this solid is that weight-average molecular weight is the polymkeric substance of 9000 (calculating with polystyrene standard), ¹³C-NMR composes (DMSO-d ₆) show that this polymkeric substance has the trimethoxysilyl (50.0ppm) that adds its end.

Embodiment 7 (polymer compound 19-23's is synthetic)

With as polymer compound 8 same way as synthesized polymer compounds 19-23, only be to use corresponding monomer to replace acrylamide and N-vinyl pyrrolidone.By ¹³C-NMR composes (DMSO-d ₆) determine that each all is the polymkeric substance that adds trimethoxysilyl (50.0ppm) at its end for these synthetic polymer compounds.In table 3, list these polymkeric substance weight-average molecular weight (calculating) that adopt gpc measurement with polystyrene standard.

Table 3

Polymer compound	Weight-average molecular weight
Polymer compound	Weight-average molecular weight	19	10000
20	8000	19	10000
20	8000	21	8000
22	11000	21	8000
22	11000	23	12000

According to the present invention, can obtain new hydrophilic polymer, it can be used for various coating effectively, comprising the coating of anti-fog coating and anti-external contamination.

[surface-modified-particulate synthesizes embodiment 1]

Adopt the particulate (S-1) of following method synthetic surface-modification, it contains the silicon dioxide microparticle of its surface with the hydrophilic polymer modification, and this polymkeric substance has silane coupling end group.

(hydrophilic polymer (P-1) (=polymer compound 1) synthetic) with silane coupling end group

Add 25 gram acrylamides, 3.5 gram 3-sulfydryl propyl trimethoxy silicanes and 51.3 gram dimethyl formamides toward three-necked bottle.Under nitrogen gas stream, this mixture heating up to 65 ℃, again toward wherein add 0.25 gram 2,2 '-azo two (2, the 4-methyl pentane nitrile) is with initiation reaction.This reaction mixture stirred 6 hours, and then cool to room temperature is poured in 1.5 liters of vinyl acetic monomers then.As a result, separate out solid.This solid separates after filtration, uses the vinyl acetic monomer thorough washing, dry then (output: 21 grams).GPC shows that this solid is that weight-average molecular weight is the polymkeric substance of 5000 (calculating with polystyrene standard).

(synthesizing of surface-modified silicon dioxide microparticle (S-1))

Add 10 gram fine silica particulates (Sylysia 350, produced by Fuji SilysiaChemical Ltd.), 8 toward homogenizer and restrain hydrophilic polymer, 1 gram benzo oxa-silepine dimethyl ester, 5 gram 25% ammonia soln and 200 milliliters of toluene with silane coupling end group.These contents mixed 1 hour with 18000 rev/mins.

The mixture that obtains is put into bottle, this bottle configuration agitator, prolong and the trap that is used to dewater, heated and stirred 2 hours under the refluxing toluene temperature therein.After stirring, content is transferred to centrifuge separator, with 7000 rev/mins of centrifugations 30 minutes.Therefore, this mixture is divided into toluene solution and precipitation.With the ultra-sonic dispersion machine this precipitation is dispersed in 400 ml waters, and then carries out centrifugation, thereby washed this precipitation with centrifuge separator.This washing operation with acetone repeats twice.The precipitation that so the obtains drying of giving free rein to obtains 14.4 gram white powders (S-1).This powder is analyzed with TG-DTA (SeikoInstruments Inc. production), determines owing to organic thermogravimetric loss.As a result, observing weight loss is 12.5%.

[surface-modified-particulate synthesizes embodiment 2]

Adopt the particulate (S-2) of following method synthetic surface-modification, it contains the silicon dioxide microparticle of its surface with the hydrophilic polymer modification, and this polymkeric substance has silane coupling end group.

(hydrophilic polymer (P-2) (=polymer compound 2) synthetic) with silane coupling end group

Add 25 gram 2-acrylamido-2-methyl propane sulfonic acid, 1.2 gram 3-sulfydryl propyl trimethoxy silicanes and 52.4 gram methyl alcohol toward three-necked bottle.Under nitrogen gas stream, this mixture heating up to 60 ℃, toward wherein add 0.25 gram 2,2 '-azobis isobutyronitrile is with initiation reaction.This reaction mixture stirred 6 hours, and then cool to room temperature is poured in 1.5 liters of acetone then.As a result, separate out solid.This solid separates after filtration, uses the acetone thorough washing, dry then (output: 19 grams).GPC shows that this solid is that weight-average molecular weight is the polymkeric substance of 3500 (calculating with polystyrene standard).

(synthesizing of surface-modified silicon dioxide microparticle (S-2))

With as the particulate (S-2) of the identical method synthetic surface-modification of the synthetic embodiment of surface-modified particulate 1, only be to use hydrophilic polymer (P-2) with silane coupling end group.Particulate (P-2) output is 13.2 grams.As the thermogravimetric loss value with TG-DTA (Seiko Instruments Inc. production) measurement is 10.5%.

[surface-modified-particulate synthesizes embodiment 3]

Adopt the particulate (S-3) of following method synthetic surface-modification, it contains the silicon dioxide microparticle of its surface with the hydrophilic polymer modification, and this polymkeric substance has silane coupling end group.

(hydrophilic polymer (P-4) (polymer compound 4) synthetic) with silane coupling end group

Add 50 gram N-vinyl acetamide, 5.8 gram 3-sulfydryl propyl trimethoxy silicanes and 111.5 gram N,N-DIMETHYLACETAMIDEs toward three-necked bottle.Under nitrogen gas stream, this mixture heating up to 65 ℃, again toward wherein add 0.5 gram 2,2 '-azo two (2, the 4-methyl pentane nitrile) is with initiation reaction.This reaction mixture stirred 6 hours, and then cool to room temperature is poured 2.0 liters of vinyl acetic monomers then into.As a result, separate out solid.This solid separates after filtration, uses the acetone thorough washing, dry then (output: 42 grams).GPC shows that this solid is that weight-average molecular weight is the polymkeric substance of 6000 (calculating with polystyrene standard).

(synthesizing of surface-modified silicon dioxide microparticle (S-3))

Add the 50 gram colloid silica aqueous solution (Snowtex ZL, by Nissan ChemicalIndustries, Ltd. produces) and 6 toward three-necked bottle and restrain hydrophilic polymer (P-4) with silane coupling end group.The pH regulator to 7.5 of this mixture.This mixture stirred 4 hours at 70 ℃, and then cool to room temperature is poured in 500 milliliters of acetone then.As a result, separate out solid.Solid is dry again after separating.

After the drying, the solid redispersion is in water, and dispersion liquid carries out centrifugation with centrifuge separator, to be settled out silicon dioxide microparticle.Remove supernatant liquor.This operation repeats twice with the purifying solid.So surface-modified silicon dioxide microparticle (S-3) output of purifying is 15 grams.Particulate (S-3) is analyzed with TG-DTA (SeikoInstruments Inc. production), to determine owing to organic thermogravimetric loss.As a result, observing weight loss is 19.5%.

[surface-modified-particulate synthesizes embodiment 4]

Adopt the particulate (S-4) of following method synthetic surface-modification, it contains the silicon dioxide microparticle of its surface with the hydrophilic polymer modification, and this polymkeric substance has silane coupling end group.

(hydrophilic polymer (P-5) (=polymer compound 5) synthetic) with silane coupling end group

Add 50 gram vinylformic acid, 6.8 gram 3-sulfydryl propyl trimethoxy silicanes and 114 gram N,N-DIMETHYLACETAMIDEs toward three-necked bottle.Under nitrogen gas stream, this mixture heating up to 65 ℃, again toward wherein add 0.5 gram 2,2 '-azo two (2, the 4-methyl pentane nitrile) is with initiation reaction.This reaction mixture stirred 6 hours, and then cool to room temperature is poured in 2.0 liters of vinyl acetic monomers then.As a result, separate out solid.This solid separates after filtration, uses the acetone thorough washing, dry then (output: 45 grams).GPC shows that this solid is that weight-average molecular weight is the polymkeric substance of 1500 (calculating with polystyrene standard).

(synthesizing of surface-modified silicon dioxide microparticle (S-4))

Silicon dioxide microparticle (S-4) with as the synthetic embodiment 3 same way as synthetic surface-modifications of surface-modified-particulate only is to use the hydrophilic polymer (P-5) with silane coupling end group.Particulate (S-4) output is 12.5 grams.Measuring its thermogravimetric loss with TG-DTA (Seiko Instruments Inc. production) is 18.6%.

[surface-modified-particulate synthesizes embodiment 5]

Adopt the particulate (S-5) of following method synthetic surface-modification, it contains silicon dioxide microparticle, and the hydrophilic polymer to add with the similar mode of grafting is arranged on its surface.

Add 6 gram fine silica particulates (Aerosil 200, produced by Nippon Aerosil Co.Ltd.), 4 gram 3-sulfydryl propyl trimethoxy silicane and 196 milliliters of toluene toward three-necked bottle.The mixture that obtains reacted 12 hours under the refluxing toluene temperature in nitrogen gas stream, and then cool to room temperature is poured in 1 liter of methyl alcohol then.This carbinol mixture was placed 24 hours.Thereafter, the precipitation of generation is separated after drying (output: 5.2 grams) after filtration.

Add nitric acid two ammoniums-cerous nitrate (IV) aqueous solution that the above-mentioned silicon-dioxide that obtains of 4 grams, 72 milliliter of 4.7 mol acrylamide solution and 8 milliliter of 0.2 mol prepare with 1 mol aqueous nitric acid toward three-necked bottle.The mixture that obtains 30 ℃ of reactions 1 hour, is poured in 1 liter of acetone in nitrogen gas stream then.As a result, separate out solid.This solid carries out drying after separating.

After the drying, this solid redispersion is in water, and dispersion liquid carries out centrifugation with separating centrifuge, to be settled out silicon dioxide microparticle.Remove supernatant liquor.This operation repeats twice with the purifying solid.So surface-modified particulate (S-5) output of purifying is 3.5 grams.Analyze particulate (S-5) with TG-DTA (Seiko Instruments Inc. production), so that determine owing to organic thermogravimetric loss.As a result, observed weight loss is 20.5%.

[surface-modified-particulate synthesizes embodiment 6]

Adopt the particulate (S-6) of following method synthetic surface-modification, it contains silicon dioxide microparticle, and the hydrophilic polymer to add with the similar mode of grafting is arranged on this surface.

Adopt the same procedure of synthetic embodiment 5, only be to use 2-acrylamido-2-methyl propane sulfonic acid aqueous solution to replace acrylamide solution, the particulate of synthetic surface-modification (S-6), it contains silicon dioxide microparticle, and the hydrophilic polymer to add with the similar mode of grafting is arranged on this surface.Particulate (S-6) output is 3.1 grams.As measure its thermogravimetric loss with TG-DTA (Seiko Instruments Inc. production) is 19.3%.

Embodiment 8 (positive photosensitive Lighographic printing plate precursor)

(generation of hydrophilic layer)

Add 3 gram methyl alcohol toward the surface-modified particulate (S-1) of 1 gram.Mixture that obtains and granulated glass sphere one are reinstated coating vibrator vibration 30 minutes, to obtain the methyl alcohol dispersion liquid of surface-modified particulate (S-1).Add 0.3 gram tetraethoxysilane and 0.06 gram phosphoric acid/water (1: 1 by weight) toward this dispersion liquid.This mixture at room temperature stirs and made its hydrolysis in 20 minutes.Therefore, obtain uniform dispersion liquid.

The dispersion liquid that obtains is coated on the pet film carrier with the 10# rod, 250 microns (360 gram/rice of its film thickness ²), be coated with hydrocolloid adhesive layer on it.The dispersion liquid of coating obtains hydrophilic layer 100 ℃ of dryings 10 minutes.The contact angle of having measured resultant hydrophilic layer (drips in water in air; CA-Z is produced by Kyowa Kaimen Kagaku K.K.), measurement is 10 °.

Then on the hydrophilic layer that so generates, form imaging layer as positive photosensitive coating, to obtain the positive photosensitive Lighographic printing plate precursor.This plate precursor is exposed, and colour developing revalues its printing performance.

[composition of imaging layer]

(alkali-insoluble polymer may/naphthoquinones-1,2-diazide composition (common positive composition))

By 0.9 gram naphthoquinones-1, and the novolac resin that the ester of 2-two nitrine-4-SULPHURYL CHLORIDE and pyrogallol-acetone resin, 0.05 gram Victoria pure blue B OH, 2.0 grams are obtained by cresols and formaldehyde (: right=6: 4; Weight-average molecular weight, 1800), the composition formed of 20 gram methylethylketones and 7 gram methyl alcohol, be applied on this hydrophilic layer.Therefore, obtained the positive photosensitive Lighographic printing plate precursor of embodiment 8.

The positive photosensitive Lighographic printing plate precursor of the embodiment 8 that so obtains is accepted the PS rayed by the stepping deflector roll of being produced by Fuji Photo Film Co.Ltd., uses the automatic processor of being produced by Fuji Photo Film Co.Ltd. that developer DP-4 (1: 8) is housed to handle then.Then print with KOR-D type Heidel printing press.As a result, obtain 5000 gratifying printed matters, wherein the nonimaging district does not have dirt.

Embodiment 9-12

Operate equally as embodiment 8, only be to use every kind of particular surface-material modified conduct particulate of hydrophilic polymer modification of listing in the following table 4.Therefore, produce the photosensitive planographic plate precursor.These plate precursor are shone, and colour developing revalues printing performance.What obtain the results are shown in the following table 4.

Table 4

Embodiment	Surface modified particulate	Hydrophilic layer contact angle (degree)	Printing performance (5000 printing dirts)
Embodiment	Surface modified particulate	Hydrophilic layer contact angle (degree)	Printing performance (5000 printing dirts)	9	S-3	9	No dirt
10	S-4	12	No dirt	9	S-3	9	No dirt
10	S-4	12	No dirt	11	S-5	15	No dirt
12	S-6	8	No dirt	11	S-5	15	No dirt

Embodiment 13

The minus precursor of thermosensitive lithographic printing plate

Use carrier and the hydrophilic layer same as embodiment 8.The composition that coating is pointed out below generates heat-sensitive layer as imaging layer, and to obtain the minus precursor of thermosensitive lithographic printing plate, it is shone, and printing performance is estimated in colour developing then again.

[linking agent A's is synthetic]

Dissolving 20 gram 1-[Alpha-Methyl-α-(4-hydroxy phenyl) ethyls in 100 milliliters of potassium hydroxide aqueous solutions (10%)]-4-[α, α-two (4-hydroxy phenyl) ethyl] benzene.Under stirring at room, in 1 hour, add 60 milliliters of formalin (37%) toward this solution.This reaction mixture is restir 6 hours at room temperature, pours aqueous sulfuric acid then into, makes its crystallization.The pulpous state precipitation water thorough washing that obtains is used 30 ml methanol recrystallizations then.Therefore, obtain white powder (output 20 grams).

NMR composes demonstration, and the compound that obtains is 1-[Alpha-Methyl-α-(4-hydroxy phenyl) ethyl]-4-[α, α-two (4-hydroxy phenyl) ethyl] the hexamethylol compound of benzene.With reversed-phase HPLC (post, Shimpac CLC-ODS (production of Tianjin, island company); Solvent, methanol=60/40 is to 90/10) measure, this hexamethylol compound purity is 92%.Under heating, this hexamethylol compound of 20 grams is dissolved in 1000 ml methanol.Toward wherein adding 1 milliliter of vitriol oil, the mixture heating up that obtains refluxed 12 hours, then cooling.After this, toward wherein adding 2 gram salt of wormwood, stir this mixture, reconcentration.Add 300 milliliters of vinyl acetic monomers toward enriched material.The mixture that obtains washes with water, and is dry again, boils off solvent then.As a result, obtain white solid (output 22 grams).

The compound that discovery obtains is 1-[Alpha-Methyl-α-(4-hydroxy phenyl) ethyl]-4-[α, α-two (4-hydroxy phenyl) ethyl] the hexamethoxy methyl compound of benzene.With reversed-phase HPLC (post, Shimpac CLC-ODS (production of Tianjin, island company); Solvent, methanol=60/40 is to 90/10) measure, this hexamethoxy methyl compound purity is 90%.

[imaging layer composition]

Restrain IRG22 (by Nippon Kayaku Co by 0.1, Ltd. the Infrared dyes of Sheng Chaning), 0.21 gram linking agent A, the novolac resins (weight-average molecular weight 12000) of 2.1 gram P-Fs, 0.02 gram 9,10-dimethoxy anthracene sulfonic acid xenyl iodine, 0.06 gram Megafac F-176 are (by Dainippon Ink ﹠amp; The fluorine chemistry tensio-active agent that Chemicals, Inc. produce), 15 gram methylethylketones and the 12 gram 2-compositions that methoxyl group-1-propane is formed are applied on the same as in the previous examples carrier.Therefore, obtain the minus precursor of thermosensitive lithographic printing plate of embodiment 13.

The minus precursor of thermosensitive lithographic printing plate of the embodiment 13 that so obtains is with semiconductor laser (wavelength, 825nm, beam diameter, 1/e ²=6 microns) as the heat pattern laser apparatus, export under the 110 milliwatt conditions at linear speed 8 meter per seconds and polar board surface and to shine.After the irradiation, plate precursor uses the automatic processor of all being produced by Fuji Photo Film Co.Ltd. that developer DP-4 (1: 8) and rinsing liquid FR-3 (1: 7) are housed to handle 110 ℃ of thermal treatments 1 minute then.Then, the version surface uses the gummy GU-7 (1: 1) that is produced by Fuji Photo Film Co.Ltd. to handle.Print with KOR-D type Heidel printing press.As a result, obtain 6000 printed matters, wherein the nonimaging district does not have dirt.

Then, the minus precursor of thermosensitive lithographic printing plate of embodiment 13 stores for 75% time with relative humidity at 45 ℃, carries out same processing then.As a result, this press plate can also obtain gratifying printed matter, and wherein the nonimaging district does not have dirt.The printed matter amount that obtains like this is 5000.

Lithographic plate ground of the present invention comprises carrier, the hydrophilic layer that forms on it, this hydrophilic layer contains solia particle, hydrophilic polymer and this microparticle surfaces direct chemical bonding, and the polymer compound that hydrophilic functional groups is arranged, this lithographic plate ground has following advantage.By form suitable sensitive layer at hydrophilic layer, can obtain splendid wetting ability, also do not damage the intensity of film.This press plate ground can be given in the lithographic plate that the aspect of performance of not tracking down and recover stolen goods improves especially greatly, even gives the printed matter of not tracking down and recover stolen goods under strict printing condition.

Claims

1, a kind of polymer compound, it contains:

I) usefulness-(CHR ³-CR ⁴(-L-Y))-expression polymerized unit; With

Ii) use-S-(CH ₂) _n-Si-(R ¹) _m(OR ²) _3-mThe silane coupling group of expression, as polymer terminal group,

R wherein ¹, R ², R ³And R ⁴Represent hydrogen atom separately or have the alkyl of 1-8 carbon atom; M represents 0,1 or 2; N represents the integer among the 1-8; L represents singly-bound or following linking group:

-CH ₂- -O-

-S- -NH-

Y representative-N (R ⁷) (R ⁸) ,-OH ,-NHCOR ⁷,-COR ⁷,-CO ₂M or-SO ₃M, wherein R ⁷And R ⁸Represent hydrogen atom separately or have the alkyl of 1-8 carbon atom; M represent hydrogen atom, basic metal, alkaline-earth metal or; The weight-average molecular weight of this polymer compound is 1000-100000.

2, a kind of lithographic plate ground, it contains: carrier, contain hydrophilic layer, the described polymer compound of claim 1 and this solia particle chemical bonding of solia particle.

3, lithographic plate ground according to claim 2, it also contains undercoat between carrier and hydrophilic layer.

4, lithographic plate ground according to claim 2, wherein carrier has coarse surface.

5, lithographic plate ground according to claim 2, wherein solia particle is an inorganic particles.

6, lithographic plate ground according to claim 5, wherein the mean particle size of inorganic particles be 10 microns or below.

7, lithographic plate ground according to claim 2, wherein hydrophilic polymer has the silane coupling group as its end group, and silane coupling group and solia particle surface chemistry bonding.

8, lithographic plate ground according to claim 2, wherein the thickness of hydrophilic layer is 0.001-10 gram/rice ²

9, lithographic plate ground according to claim 2, wherein undercoat contains hydrophile adhesive mass and silicon-dioxide.